KR20150059340A - Polylactic acid/acrylonitrile-butadiene-styrene copolymer alloy resin composition - Google Patents

Abstract

The present invention relates to a polylactic acid/acrylonitrile-butadiene-styrene copolymer alloy resin composition including: (1) 30 to 90 parts by weight of a polylactic acid resin; and (2) 70 to 10 parts by weight of the acrylonitrile-butadiene-styrene copolymer resin. The (1) polylactic acid resin includes: a hard segment including a polylactic acid repeating unit of chemical formula 1; and a soft segment including a polyolefin-based repeating unit where polyolefin-based polyol constituent units of chemical formula 2 are linearly or basinally connected with a urethane combination or an ester combination as a medium. The present invention relates to the polylactic acid/acrylonitrile-butadiene-styrene copolymer alloy resin composition which has greater than or equal to 60 weight% of an organic carbon content (%Cbio) of a biomass origin defined as a math formula 1. According to the present invention, the polylactic acid/acrylonitrile-butadiene-styrene copolymer alloy resin composition enables to show improved impact resistance, and to be usefully used as a material of a shaped product since superb general properties such as thermal resistance, water resistance, a mechanical property, injection machinability, etc. are excellent, as well as significantly contributing to preventing environmental pollution with an eco-friendly feature.

Description

POLYLACTIC ACID / ACRYLONITRILE-BUTADIENE-STYRENE COPOLYMER ALLOY RESIN COMPOSITION Technical Field [1] The present invention relates to a polylactic acid / acrylonitrile-butadiene-

More particularly, the present invention relates to a polylactic acid / acrylonitrile-butadiene-styrene copolymer resin composition which not only exhibits an improved impact strength but also has various physical properties such as heat resistance, moisture resistance, mechanical properties and injection- Butadiene-styrene copolymers, which can be effectively used as a molded article material, and which are environmentally friendly, and a resin composition comprising an acrylonitrile-butadiene-styrene copolymer.

Crude oil-based resins such as polyethylene terephthalate, nylon, polyolefin or flexible polyvinyl chloride (PVC) are still widely used as materials for various applications such as packaging materials. However, these crude oil-based resins do not have biodegradability and thus have a problem of causing environmental pollution such as a large amount of carbon dioxide, which is a global warming gas, when they are disposed of. Further, as the petroleum resources gradually become depleted, the use of biomass-based resins, typically polylactic acid resins, has been widely studied.

However, these polylactic acid resins are insufficient in heat resistance, moisture resistance, and mechanical properties compared to crude oil-based resins, and therefore, there is a limit to fields or applications to which they can be applied. Particularly, attempts have been made to apply poly (lactic acid) resin as a packaging material for packaging films and the like, but such applications are limited due to the low flexibility of the poly (lactic acid) resin.

In order to overcome the limitations of such polylactic acid resins, polylactic acid resins and other general-purpose resins and / or alloying-type compositions of engineering plastics are used. However, even when a molded article containing a polylactic acid resin is obtained by using such a composition in the form of a ring, in most cases, compatibility problems between the two resins have been limited in improving heat resistance and mechanical properties.

In addition, recently, a method of introducing a graft copolymer compatibilizer into a polylactic acid resin in order to solve the above problems has been proposed (Korean Patent Laid- 2012-0041626 and 2011-0000247). However, polylactic acid resin compositions and products using such graft copolymer compatibilizers or glycidyl methacrylate reactive compatibilizers are problematic in that the cost of the compatibilizing agent is high, and when the polylactic acid resin and the acrylonitrile-butadiene- There is a limit in overcoming the low compatibility of the rhenylene copolymer so that the effect of improving the physical properties is not sufficient and it is difficult to apply the rhenylene copolymer as an automotive interior material requiring high durability. In addition, such a polylactic acid resin composition has a wide molecular weight distribution, poor melting property, poor molding injection state, poor appearance of the product, and insufficient mechanical properties, heat resistance and impact resistance. In addition, the compatibilizers generate volatile organic compounds due to residual solvents, monomers, and thermal decomposition products upon compounding, thereby generating a large amount of total volatile organic compounds (TVOCs). Among these volatile organic compounds, compounds of toluene, xylene, styrene, or alkanes of 5 to 12 carbon atoms have a strong irritating odor, and when a person is exposed to the air containing such total volatile organic compounds for a long time, Drowsiness, motion sickness, shortness of breath, eye, nose, and neck pain may be harmful.

The polylactic acid resin generally has a very weak moisture resistance, which is mainly caused by a hydrolysis reaction of water contained in the resin. As a result, a part of the polymer is decomposed into lactic acid, a monomer or an oligomer, Degradation occurs.

Furthermore, the resulting lactic acid, monomers and oligomers volatilize during the molding process of the resin, leading to contamination and corrosion of the machine and also to quality problems of the molded product. Specifically, in the case of sheet production by extrusion molding, residual lactic acid, monomer and oligomer remaining in the resin are volatilized during sheet extrusion, resulting in a variation in thickness of a sheet to be produced. In the case of injection molded articles, Hydrolysis may occur and deterioration of mechanical properties may occur. In addition, due to the nature of the poly (lactic acid) resin, the water absorption is very easy, so that the water absorption in the pellet state during the operation of the water bath for cooling after passing through the extruder, Injection of a molded product may cause defects such as appearance of silver streak due to moisture in the resin and deterioration of physical properties.

Accordingly, there is a continuing demand for development of a poly (lactic acid) resin which exhibits improved impact resistance, is excellent in moisture resistance, and has excellent physical properties such as mechanical properties, heat resistance and bleeding-out properties, It is required to develop a technique capable of reducing the amount of generated volatile organic compounds and maintaining the physical properties of the resin itself.

Korean Patent Publication No. 2012-0041626 Korean Patent Publication No. 2011-0000247

INDUSTRIAL APPLICABILITY The present invention is not limited to a polyolefin resin which exhibits improved impact resistance and is excellent in various physical properties such as moisture resistance, mechanical properties, transparency, heat resistance, blocking resistance and molding processability, Lactic acid / lactone / acrylonitrile / butadiene / styrene copolymer alloy resin composition.

In accordance with the above object,

Acrylonitrile-butadiene-styrene copolymer block copolymer composition comprising (1) 30 to 90 parts by weight of a polylactic acid resin and (2) 70 to 10 parts by weight of an acrylonitrile-butadiene-styrene copolymer resin as,

The polylactic acid resin (1) comprises a hard segment comprising a polylactic acid repeating unit represented by the following formula (1), and a polyolefin-based polyol constituent unit represented by the following formula (2) in a linear or branched Based polyol repeat units,

A polylactic acid / acrylonitrile-butadiene-styrene copolymer alloy resin composition having an organic carbon content (% C _bio ) of biomass origin defined by the following formula (1) is 60% by weight or more:

[Equation 1]

% C = _Bio (poly ¹⁴ C isotope ratio by weight of the ¹² C isotope of carbon atoms of the lactic acid resin) / ⁽¹⁴ C isotope ratio by weight of the ^bio-12 C isotope of carbon atoms of the mass origin standard)

In the general formulas (1) and (2), n is an integer of 700 to 5,000 and m + 1 is an integer of 5 to 200.

The polylactic acid / acrylonitrile-butadiene-styrene copolymer alloy resin composition according to the present invention not only exhibits improved impact resistance but also has excellent physical properties such as heat resistance, moisture resistance, mechanical properties and injection processability, It can be usefully used, and since it has environment-friendly characteristics, it can contribute to prevention of environmental pollution.

1 to 3 are electron micrograph (SEM) photographs of the pellets prepared in Examples 1 to 3, respectively.

Hereinafter, the polylactic acid / acrylonitrile-butadiene-styrene copolymer alloy resin composition according to a specific embodiment of the present invention will be described.

The polylactic acid / acrylonitrile-butadiene-styrene copolymer alloy resin composition according to the present invention comprises (1) 30 to 90 parts by weight of a polylactic acid resin, and (2) an acrylonitrile-butadiene- 10 parts by weight,

The polylactic acid resin (1) comprises a hard segment comprising a polylactic acid repeating unit represented by the following formula (1), and a polyolefin-based polyol constituent unit represented by the following formula (2) in a linear or branched Based polyol repeat units,

The organic carbon content (% C _bio ) of the biomass origin defined by the following formula (1) is 60% by weight or more:

[Chemical Formula 1]

(2)

[Equation 1]

% C = _Bio (poly ¹⁴ C isotope ratio by weight of the ¹² C isotope of carbon atoms of the lactic acid resin) / ⁽¹⁴ C isotope ratio by weight of the ^bio-12 C isotope of carbon atoms of the mass origin standard)

In the general formulas (1) and (2), n is an integer of 700 to 5,000 and m + 1 is an integer of 5 to 200.

(1) Polylactic acid resin

The polylactic acid resin contained in the polylactic acid / acrylonitrile-butadiene-styrene copolymer alloy resin composition according to the present invention basically contains the polylactic acid repeating unit represented by the above formula (1) as a hard segment. In addition, the poly (lactic acid) resin includes a polyolefin-based polyol repeating unit as a soft segment. In the polyolefin-based polyol repeating unit, the polyolefin-based polyol constitutional units represented by the formula (2) ) Or an ester bond (-C (= O) -O-).

These polylactic acid resins can basically exhibit biodegradability and environmentally friendly characteristics peculiar to biomass-based resins by including polylactic acid repeating units as hard segments. Further, as a result of the experiments conducted by the inventors of the present invention, it has been found that the inclusion of the polyolefin-based polyol repeating unit as a soft segment makes it possible to produce a molded article exhibiting greatly improved flexibility using the polylactic acid resin as well as exhibiting excellent transparency and low haze value . Particularly, since such a soft segment is introduced into the polylactic acid resin itself in a form combined with the hard segment, there is less concern that the soft segment for improving the flexibility is bleed out or exhibits low stability, and the molded product including the polylactic acid resin It was confirmed that the haze was increased or the transparency was lowered. In addition, the poly (lactic acid) resin can exhibit the above-described effects without increasing the soft segment content for improving flexibility. Therefore, a relatively high content of a biomass-based resin, for example, a hard segment derived from a poly .

On the other hand, the polylactic acid resin has an excellent moisture resistance as compared with ordinary polylactic acid resin because it contains a non-polar soft segment.

The polylactic acid resin contained in the polylactic acid / acrylonitrile-butadiene-styrene copolymer alloy resin composition preferably has an organic carbon content (% C _bio ) of biomass origin defined by the above formula (1) , At least about 70 wt%, at least about 80 wt%, at least about 85 wt%, at least about 90 wt%, or at least about 95 wt%.

Unlike the polylactic acid resin contained in the polylactic acid / acrylonitrile-butadiene-styrene copolymer alloy resin composition of the present invention, the polylactic acid resin contains a polyester-based repeating unit other than the polyolefin-based polyol repeating unit as a soft segment In the case of the poly (lactic acid) resin, it is necessary to introduce another resin such as a polyester polyol repeating unit having a higher content of fossil fuel origin in order to achieve excellent flexibility. Therefore, the above-mentioned organic carbon content (% C _Bio ) can be difficult to achieve.

The organic carbon content (% C _bio ) of the biomass origin according to Equation 1 can be measured by, for example, the method described in the ASTM D6866 standard. The technical meanings and measurement methods of the organic carbon content (% C _bio ) will be described in more detail as follows.

In general, unlike organic materials such as resins derived from fossil raw materials, organic materials such as resins derived from biomass (biomass) are known to contain isotope ^14C . More specifically, all organic materials taken from living organisms such as animals or plants contain ¹² C (about 98.892 wt%), ¹³ C (about 1.108 wt%) and ¹⁴ C (about 1.2 x 10 ^-10 wt% , And it is known that the ratio of each isotope is kept constant. This is equal to the ratio of each isotope in the atmosphere, and this isotope ratio remains constant, as living organisms continue to metabolize and continuously exchange carbon atoms with the external environment.

)의 경과에 따라 그 함량이 감소할 수 있다. On the other hand, ¹⁴ C is a radioactive isotope,

), The content thereof may decrease.

&Quot; (2) "

는 ¹⁴C 동위원소의 초기 원자수를 나타내고, 상기

은

시간 후에 잔존하는 ¹⁴C 동위원소의 원자수를 나타내며, 상기

는 반감기와 관련된 붕괴 상수(또는 방사성 상수)를 나타낸다. In the above Equation 2,

Represents the initial number of atoms of the ¹⁴ C isotope,

silver

Represents the number of atoms of the ¹⁴ C isotope remaining after the time,

Represents the decay constant (or radioactive constant) associated with half-life.

In this equation (2), the half-life of the ¹⁴ C isotope is about 5,730 years. Considering this half-life, organic matter, such as resin derived from biomass (biomass), taken from a living organism that continually interacts with the external environment, has a substantially constant ¹⁴ It is possible to maintain a constant content ratio (weight ratio) of C isotope content and a constant content ratio with other isotopes such as ¹⁴ C / ¹² C = about 1.2 × 10 ^-12 .

On the other hand, fossil fuels such as coal or petroleum have been blocked from carbon exchange with the external environment for over 50,000 years. Accordingly, a resin such as an organic material derived from the fossil raw material is when estimated according to the equation (2), comprising the ¹⁴ C isotope in more than 0.2% of the initial content (atomic number), substantially containing the ¹⁴ C isotope I never do that.

As the equation (1) considering the above points, the denominator is the weight ratio of the isotope ¹⁴ C / ¹² C derived from a biomass, e.g., may be about 1.2 × 10 ^-12, molecules contained in the measurement target resin ¹⁴ C / ¹² < / RTI > C. As described above, from the fact that the carbon atom derived from the biomass maintains the isotope weight ratio of about 1.2 x 10 <" ^{12 &} gt ;, while the carbon atom derived from the fossil fuel has the substantially zero isotope weight ratio, (% C _bio ) of the total carbon atoms of biomass origin in the polylactic acid resin contained in the polylactic acid / acrylonitrile-butadiene-styrene copolymer alloy resin composition is measured by the above formula . At this time, the content of each carbon isotope and the content ratio thereof (weight ratio) are described in ASTM D6866-06 standard (standard test method for determining the biological base content of a natural substance using radioactive carbon and isotope ratio mass spectrometry analysis) And can be measured according to one of the three methods. Suitably, the carbon atoms contained in the resin to be measured may be converted into a graphite or carbon dioxide gas form, measured by a mass spectrometer, or measured by liquid scintillation spectrometry. At this time, together with the mass spectrometer, two isotopes can be separated using an accelerator for separating ¹⁴ C ions from ¹² C ions, and the content and content ratio of each isotope can be measured by a mass spectrometer. Optionally, the content and content ratio of each isotope may be determined using liquid scintillation spectroscopy, which is readily apparent to those skilled in the art, and the measurement of Equation (1) can be derived therefrom.

If the measured value of the organic carbon content (% C _bio ) of the formula (1) derived above is about 60 wt% or more, the polylactic acid resin and the polylactic acid / acrylonitrile-butadiene- The composition contains a resin and carbon derived from a larger amount of biomass, and can properly exhibit unique environmental characteristics and biodegradability.

More specifically, a poly (lactic acid) resin and a poly (lactic acid / acrylonitrile-butadiene-styrene copolymer) resin composition containing the poly (lactic acid) resin satisfying such a high organic carbon content (% C _bio ) exhibit the environment- .

Biochemicals such as poly lactic acid resins are biodegradable and have low carbon dioxide emissions and can reduce CO2 emissions by up to 108% compared to petrochemical products at present technology level and reduce energy for resin manufacturing by up to 50% can do. In addition, the use of biomass raw materials to produce bioplastics can reduce carbon dioxide emissions calculated by ISO 14000 compliant Life Cycle Analysis (LCA) by up to 70% compared to the use of fossil raw materials.

As a concrete example, according to NatureWorks, when producing PET resin, 3.4 kg of carbon dioxide is emitted per kg, while the polylactic acid resin, which is a kind of bio-plastic, generates only about 77 kg of carbon dioxide per kg, It can reduce carbon dioxide, and it is known that energy consumption is only 56% of PET. However, in the case of a previously known poly (lactic acid) resin, application is limited due to low flexibility and the like, and when other components such as a plasticizer are included in order to solve this problem, there is a problem that the advantages as the bioplastics described above are greatly reduced.

However, the polylactic acid resin and the polylactic acid / acrylonitrile-butadiene-styrene copolymer alloy resin composition containing the polylactic acid resin and the polylactic acid / acrylonitrile-butadiene-styrene copolymer resin composition containing the polylactic acid resin are excellent in _bioplastics It can solve the problems such as low flexibility of poly (lactic acid) resin and can be applied to various fields.

Therefore, the polylactic acid resin satisfying the above-mentioned high organic carbon content (% C _bio ) and the polylactic acid / acrylonitrile-butadiene-styrene copolymer alloy resin composition containing the same, It can exhibit eco-friendly characteristics that greatly reduce energy consumption. Such environmentally-friendly properties can be measured, for example, by life cycle assessment of a polylactic acid / acrylonitrile-butadiene-styrene copolymer alloy resin composition.

In the polylactic acid / acrylonitrile-butadiene-styrene copolymer alloy resin composition, the polylactic acid resin preferably has a content of ¹⁴ C isotopes in carbon atoms of about 7.2 x 10 ^-11 to 1.2 x 10 ^-10 wt% About 9.6 × 10 ^-11 to 1.2 × 10 ^-10 % by weight, or about 1.08 × 10 ^-10 to 1.2 × 10 ^-10 % by weight. Polylactic acid resin having such a content of ¹⁴ C isotopes can originate from more resins and carbon, or substantially all of resin and carbon, and can exhibit better biodegradability and environmentally friendly characteristics.

In the polylactic acid resin, not only the hard segment polylactic acid repeating unit is derived from the biomass, but the soft segment polyolefin polyol constituent unit may also be derived from the biomass. Such a polyolefin-based polyol constituent unit can be obtained, for example, from a polyolefin-based polyol resin derived from biomass. The biomass can be any plant or animal resource, such as a plant resource such as corn, sugarcane, or tapioca. Thus, the polylactic acid resin containing the polyolefin-based polyol constituent unit derived from biomass and the polylactic acid / acrylonitrile-butadiene-styrene copolymer alloy resin composition containing the same have higher organic carbon content (% C _bio ), Such as at least about 90% by weight, or at least about 95% by weight organic carbon content (% C _bio ).

At this time, in the polylactic acid resin, the hard segment derived from the biomass has an organic carbon content (% C _bio ) of biomass origin defined by the above-mentioned formula (1) is about 90% by weight or more, Wt%, and the soft segment derived from the biomass has an organic carbon content (% C _bio ) of biomass origin as defined in Equation 1 of not less than about 70 wt%, preferably about 75 to 95 wt% Lt; / RTI >

The polylactic acid resin contained in the polylactic acid / acrylonitrile-butadiene-styrene copolymer alloy resin composition has an organic carbon content (% C _bio ) of biomass origin of at least about 60% by weight, or at least about 80% by weight , It can meet the criteria for obtaining the "Biomass Pla" certification of JBPA, a certification based on the standard ASTM D6866. Thus, the polylactic acid resin can properly adhere to the "Biomass-based" label of JORA.

In the polylactic acid resin, the polylactic acid repeating unit of formula (1) contained in the hard segment may refer to a polylactic acid homopolymer or a repeating unit constituting the same. Such polylactic acid repeating units can be obtained by a method for producing polylactic acid homopolymers well known to those skilled in the art. For example, L-lactide or D-lactide is produced from L-lactic acid or D-lactic acid as a cyclic double monomer and is subjected to ring-opening polymerization, or a method of direct dehydration condensation polymerization of L-lactic acid or D- Among them, a polylactic acid repeating unit having a higher degree of polymerization can be obtained through ring-opening polymerization. The polylactic acid repeating unit may be prepared so as to have amorphous properties by copolymerizing L-lactide and D-lactide at a certain ratio. However, in order to further improve the heat resistance of the molded article containing the polylactic acid resin, L-lactide, or D-lactide. More specifically, the polylactic acid repeating unit can be obtained by ring-opening polymerization using an L-lactide or D-lactide raw material having an optical purity of 98% or more. When the optical purity is less than the above range, the melting temperature (Tm) Can be lowered.

On the other hand, the polyolefin-based polyol repeating units included in the soft segment of the poly (lactic acid) resin are those in which the polyolefin-based polyol structural units of the above-mentioned formula (2) are bonded by a urethane bond (-C (= O) -NH-) ) -O-). Specifically, the polyolefin-based polyol constituent unit may be a polymer obtained by conjugating a monomer such as butadiene (such as a poly (1,2-butadiene) or poly 1,3-butadiene), or a constituent unit thereof, refers to a hydroxyl-terminated polybutadiene (HTPB) having a molecular weight of 1,000 to 5,000 obtained by hydrogenating a hydroxyl group at the terminal thereof.

At this time, the urethane bond can be formed by a reaction between a hydroxyl group at the end of the polyolefin-based polyol structural unit or a prepolymer obtained by addition polymerization of a lactide to the hydroxy group at the end of the polyolefin-based polyol structural unit and a diisocyanate or an isocyanate compound having two or more functional groups (-C (= O) -O-) when the hydroxyl group at the end of the polyolefin-based polyol constituent unit is reacted with the lactide or the lactic acid derivative compound. The polyolefin-based polyol structural units may be connected to each other linearly or in a branched manner via the urethane bond or the ester bond to form the polyolefin-based polyol repeating unit.

The reaction molar ratio of the hydroxy group at the end of the polyolefin-based polyol structural unit to the isocyanate group of the diisocyanate or the isocyanate compound having two or more functional groups may be from 1: 0.50 to 1: 0.99. Preferably, the reaction molar ratio of the isocyanate group of the terminal hydroxyl group: isocyanate compound of the polyolefin-based polyol structural unit may be from about 1: 0.60 to about 1: 0.95, more preferably from about 1: 0.70 to about 1: 0.90.

The polymer formed by linking the polyolefin-based polyol structural units linearly via an urethane bond, or the repeating unit constituting the polymer, may be referred to as a polyurethane polyol repeating unit, and may have a hydroxyl group at the terminal thereof. Accordingly, the polyolefin-based polyol repeating unit can act as an initiator in the polymerization process for the formation of the polylactic acid repeating unit. However, if the molar ratio of the hydroxyl group to the isocyanate group is excessively high, the number of terminal hydroxyl groups in the polyurethane polyol repeating unit is insufficient (OHV <1), and the polyurethane polyol repeating unit may not function properly as an initiator. If the molar ratio of the hydroxyl group to the isocyanate group is too low, the number of terminal hydroxyl groups of the polyolefin-based polyol repeating unit becomes too large (OHV &gt; 35), making it difficult to obtain a polyunsaturated fatty acid repeating unit and a polylactic acid resin.

The polymer of the polyolefin-based polyol repeating unit may have a number average molecular weight of about 1,000 to 100,000, preferably about 10,000 to 50,000. If the molecular weight of the polymer of the polyolefin-based polyol repeating unit is excessively large or small, the flexibility of the molded article obtained from the polylactic acid resin and the poly (lactic acid / acrylonitrile-butadiene-styrene copolymer) Moisture resistance and mechanical properties may become insufficient. In addition, since the polylactic acid resin may be difficult to meet appropriate molecular weight characteristics and the like, the processability of the polylactic acid / acrylonitrile-butadiene-styrene copolymer alloy resin composition may deteriorate or the flexibility, moisture resistance, The physical properties may be deteriorated.

The isocyanate compound capable of bonding with the terminal hydroxyl group of the polyolefin-based polyol repeating unit to form a urethane bond may be any compound having two or more isocyanate groups in the molecule, and may be derived from a fossil fuel.

Examples of the diisocyanate compound include 1,6-hexamethylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 1,3-xylene diisocyanate, 1,4-xylene diisocyanate, , 5-naphthalene diisocyanate, m-phenylenediisocyanate, p-phenylenediisocyanate, 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, 4,4'- bisphenylenediisocyanate, hexamethylene di Isocyanurate, isocyanate, isophorone diisocyanate or hydrogenated diphenylmethane diisocyanate, and examples of the polyisocyanate compound having an isocyanate group equivalent of at least 3 include an oligomer of the diisocyanate compound, a polymer of the diisocyanate compound, a diisocyanate compound Of cyclic oligomers, hexamethylene diisocyanate isocyanurate diisocyanate isocyanurate, triisocyanate compounds, and isomers of these isocyanate compounds. Various diisocyanate compounds well known to those skilled in the art can be used without limitation. However, 1,6-hexamethylene diisocyanate is preferable from the viewpoint of imparting flexibility to molded products of polylactic acid resin.

On the other hand, the polylactic acid resin is preferably a block copolymer in which the terminal carboxyl group of the polylactic acid repeating unit contained in the hard segment is connected to the terminal hydroxy group of the polyolefin-based polyol constituent unit contained in the soft segment by ester bonding, May include linear or branched linked block copolymers via urethane linkages.

Specifically, in such a block copolymer, the terminal carboxyl group of the polylactic acid repeating unit may form an ester bond with a terminal hydroxy group of the polyolefin-based polyol repeating unit. For example, the chemical structure of such a block copolymer can be represented by the following general formula 1:

[Formula 1]

(L) - (E) - polyolefin-based polyol repeating units (O-U-O-U-O) - (E)

[Formula 2]

Polyol repeating units (L) - (E) - Polyolefin polyol constituent units (O) - (E) - Polyester repeating units (L) Polyol constituent unit (O) - (E) -Poly lactic acid repeating unit (L)

In the general formulas 1 and 2, O represents a polyolefin-based polyol structural unit, U represents a urethane bond, and E represents an ester bond.

The polyolefin-based polyol structural unit or the repeating unit for imparting flexibility can be inhibited from bleeding out by including the block copolymer in which the polylactic acid repeating unit and the polyolefin-based polyol structural unit or the repeating unit are bonded, A poly (lactic acid resin) molded article containing a poly (lactic acid) resin can have various physical properties such as excellent moisture resistance, transparency, mechanical properties, heat resistance and blocking resistance. The molecular weight distribution, the glass transition temperature (Tg), and the melting temperature (Tm) of the poly (lactic acid) resin are determined depending on the block copolymer type at least a part of the poly (lactic acid) The mechanical properties, flexibility and heat resistance of the molded article can be further improved.

However, it is not necessary that all of the polylactic acid repeating units contained in the polylactic acid resin is in the form of a block copolymer bonded to the polyolefin-based polyol structural unit or the repeating unit, and at least a part of the polylactic acid- Or may be in the form of a poly (lactic acid) homopolymer not bonded to a polyol constituent unit or a repeating unit. In this case, the polylactic acid resin may be a block copolymer in which the terminal carboxyl group of the polylactic acid repeating unit contained in the hard segment is linked by ester bonding to the terminal hydroxyl group of the polyolefin-based polyol constituent unit contained in the soft segment, May be in the form of a mixture further comprising a polylactic acid repeating unit, i.e., a polylactic acid homopolymer, which is not bonded to the polyolefin-based polyol repeating unit, in a linear or branched block copolymer through an urethane bond.

On the other hand, based on the total 100 parts by weight of the polylactic acid resin (the weight of the block copolymer described above and, when the polylactic acid homopolymer is optionally contained, 100 parts by weight in total with such a homopolymer) About 65 to 95 parts by weight, about 80 to 95 parts by weight, or about 82 to 92 parts by weight of the hard segment, about 5 to 35 parts by weight, about 5 to 20 parts by weight, or about 8 to 18 parts by weight of the soft segment .

If the content of the soft segment is excessively high, it may become difficult to provide a poly (lactic acid) resin having a high molecular weight, and mechanical properties such as strength of the molded article containing the poly (lactic acid) resin may be deteriorated. In addition, the glass transition temperature is lowered, and slipping, handling property or shape retaining property may be deteriorated during packaging using a molded article. On the other hand, if the content of the soft segment is excessively low, there is a limit to improve the flexibility and moisture resistance of the molded article including the poly (lactic acid) resin and the poly (lactic acid) resin. Particularly, the glass transition temperature of the poly (lactic acid) resin becomes too high, and the flexibility of the molded product may be deteriorated. Since the polyolefin-based polyol structural unit or the repeating unit of soft segment is difficult to act as an initiator, The resin may not be manufactured properly.

The polylactic acid resin in the above-described polylactic acid / acrylonitrile-butadiene-styrene copolymer alloy resin composition may have a number average molecular weight of about 50,000 to 200,000, preferably a number average molecular weight of about 50,000 to 150,000. The poly (lactic acid) resin may have a weight average molecular weight of about 100,000 to 400,000, preferably a weight average molecular weight of about 100,000 to 320,000. Such a molecular weight may affect the workability of the above-mentioned poly (lactic acid / acrylonitrile-butadiene-styrene copolymer) resin composition and the mechanical properties of the molded article. When the molecular weight is too small, the melt viscosity is too low when melt-processed by a method such as extrusion and the workability in a molded product or the like may be deteriorated, and the mechanical properties such as strength may be lowered even if it can be processed into a molded product. On the other hand, when the molecular weight is excessively high, the melt viscosity during melt processing is too high, and productivity and workability as a molded product may be greatly reduced.

The polylactic acid resin may have a molecular weight distribution (Mw / Mn) of about 1.60 to 3.0, preferably about 1.80 to 2.15, which is defined as a ratio of a weight average molecular weight (Mw) to a number average molecular weight (Mn). As the poly (lactic acid) resin exhibits such a narrow molecular weight distribution, it exhibits an appropriate melt viscosity and melting property when it is melt processed by a method such as extrusion and can exhibit an excellent molded article extrusion state and processability, Can exhibit excellent mechanical properties such as strength. In contrast, when the molecular weight distribution is too narrow, the melt viscosity at the processing temperature for extrusion or the like is excessively large, which may result in difficulty in processing as a molded product. Conversely, if the molecular weight distribution is excessively widened, The melt viscosity may become too small and the melt property may be poor, which may make the molding itself difficult or the molded extrusion state may not be good.

Further, the polylactic acid resin may have a melting temperature (Tm) of about 145 to 178 ° C, about 160 to 178 ° C, or about 165 to 175 ° C. If the melting temperature is too low, the heat resistance of the molded article including the polylactic acid resin may be deteriorated. If the melting temperature is excessively high, a high temperature is required for melt processing by extrusion or the like, or the viscosity becomes too high, .

And, the polylactic acid resin, such as the block copolymer contained therein, has a glass transition temperature (Tg) of about 20 to 55 캜, or about 25 to 55 캜, or about 30 to 55 캜. As the polylactic acid resin exhibits such a glass transition temperature range, flexibility and stiffness of the molded article containing the polylactic acid / acrylonitrile-butadiene-styrene copolymer alloy resin composition are appropriately maintained, Can be preferably used. If the glass transition temperature of the poly (lactic acid) resin is too low, the flexibility of the molded article may be improved. However, as the strength becomes too low, slippage, handling property, And the like may be poor, which may make the application to a molded article unsuitable. On the other hand, if the glass transition temperature is too high, the flexibility of the molded product is low and the strength is too high, which may result in poor adhesion to the object product during assembly of the molded product.

On the other hand, the polylactic acid / acrylonitrile-butadiene-styrene copolymer alloy resin composition may contain less than about 1% by weight of a monomer (for example, a polylactic acid repeating unit , And more preferably about 0.01 to 0.5% by weight of the monomer may remain. The polylactic acid / acrylonitrile-butadiene-styrene copolymer alloy resin composition contains a block copolymer having specific structural characteristics, a polylactic acid resin containing the block copolymer and an antioxidant, Most of the monomers participate in the polymerization to form polylactic acid repeating units, and the depolymerization or decomposition of the polylactic acid resin does not substantially occur. For this reason, the polylactic acid / acrylonitrile-butadiene-styrene copolymer alloy resin composition may contain a minimized amount of residual monomers such as residual lactide monomers and the like.

If the residual monomer content is about 1% by weight or more, problems arise during molding using the polylactic acid / acrylonitrile-butadiene-styrene copolymer alloy resin composition. In addition, when the content of the polylactic acid resin The reduction of the molecular weight results in a decrease in the strength of the final molded product, and the residual monomers may be bleed-out during application for food packaging, resulting in stability problems.

(2) Acrylonitrile-butadiene-styrene copolymer resin

The acrylonitrile-butadiene-styrene copolymer resin included in the polylactic acid / acrylonitrile-butadiene-styrene copolymer alloy resin composition according to the present invention is used for reinforcing the physical properties of the polylactic acid resin, Butadiene-styrene copolymer as a main component in order to maximize physical properties such as impact strength, rigidity, durability and heat resistance of the lactic acid resin.

The acrylonitrile-butadiene-styrene copolymer (ABS) resin may include 10 to 30% by weight of acrylonitrile, 10 to 30% by weight of butadiene, and 40 to 70% by weight of styrene. If the content of acrylonitrile is 10 wt% or more, desired stiffness, oil resistance, and chemical resistance can be achieved. If the content is 30 wt% or less, desired molding processability and impact resistance can be achieved. If the content of butadiene is 10 wt% or more, desired impact resistance can be achieved. If the content of butadiene is 30 wt% or less, desired rigidity, oil resistance, and chemical resistance can be achieved. If the content of styrene is 40% by weight or more, desired molding processability can be achieved. If the content of styrene is 70% by weight or less, desired stiffness, oil resistance, chemical resistance and impact resistance can be achieved. The acrylonitrile-butadiene-styrene copolymer may further comprise a styrene-acrylonitrile copolymer (SAN), wherein the styrene-acrylonitrile copolymer (SAN) comprises 60 to 80 wt% Is graft-polymerized with 20 to 40% by weight of acrylonitrile. When the content of styrene is within the above range, sufficient physical properties of the desired composite material can be achieved by exhibiting sufficient compatibility with the acrylonitrile-butadiene-styrene copolymer. The styrene-acrylonitrile copolymer (SAN) may be used in an amount of 30 to 70 parts by weight based on 100 parts by weight of the acrylonitrile-butadiene-styrene copolymer. If the amount of the styrene-acrylonitrile copolymer (SAN) used for the acrylonitrile-butadiene-styrene copolymer is 30 parts by weight or more, sufficient physical properties can be achieved, If it is 70 parts by weight or less, sufficient impact resistance can be achieved. The acrylonitrile-butadiene-styrene copolymer may be a matrix resin of a composite material together with a polylactic acid resin, and the acrylonitrile-butadiene-styrene copolymer resin may be a polylactic acid / acrylonitrile-butadiene- It may be 10 to 70 parts by weight, preferably 30 to 60 parts by weight based on 100 parts by weight of the polyolefin resin composition of the present invention. Within this range, compatibility with the polylactic acid resin, heat resistance, It can exert strength.

The polylactic acid / acrylonitrile-butadiene-styrene copolymer alloy resin composition may further comprise an impact modifier.

Examples of the impact modifier include an olefin impact modifier, an acrylic impact modifier, a methyl methacrylate-butadiene-styrene (MBS) impact modifier, a styrene-ethylene-butadiene-styrene (SEBS) impact modifier, a silicone impact modifier, An elastomeric impact modifier, and an elastomeric impact modifier, and preferably an olefin-based impact modifier, and more preferably an ethylene-olefin-based copolymer.

The olefin-based impact modifier is excellent in compatibility with an acrylonitrile-butadiene-styrene copolymer and exhibits excellent impact resistance and is economical. Particularly, the ethylene-olefin-based copolymer has excellent elasticity, flexibility and impact resistance , The ethylene-olefin-based copolymer is preferably prepared using a metallocene catalyst.

The polylactic acid resin of the polylactic acid / acrylonitrile-butadiene-styrene copolymer alloy resin composition of the present invention is such that the polyolefin-based polyol component is introduced into the polylactic acid resin polymer structure, and an acrylic impact modifier, methyl methacrylate-butadiene - Since it shows excellent compatibility with styrene (MBS) type impact modifier, styrene-ethylene-butadiene-styrene (SEBS) type impact modifier, silicone type impact modifier and polyester elastomer impact modifier, Do not.

The impact modifier is added in an amount of 20 parts by weight or less, preferably 0.1 to 20 parts by weight, more preferably 0.1 to 20 parts by weight, based on 100 parts by weight of the total of (1) the poly (lactic acid) resin and (2) the acrylonitrile-butadiene- 5 to 10 parts by weight may be included.

Within the above range, the polylactic acid / acrylonitrile / butadiene / styrene copolymer resin composition is excellent in compatibility with the polylactic acid resin and the acrylonitrile / butadiene / styrene copolymer resin, and the impact resistance , The elongation and the heat resistance are greatly improved. Since the impact modifier lowers the crystallization speed and crystallization rate of the poly (lactic acid) / acrylonitrile-butadiene-styrene copolymer alloy resin composition to deteriorate the heat resistance and injection moldability, the amount of the impact modifier exceeds 20 parts by weight There may be a problem that the heat resistance and appearance of the injection-molded article are deteriorated.

On the other hand, the polylactic acid / acrylonitrile-butadiene-styrene copolymer alloy resin composition may contain an antioxidant. The antioxidant suppresses the yellowing of the poly (lactic acid) resin to improve the appearance of the poly (lactic acid) / acrylonitrile-butadiene-styrene copolymer resin composition and the molded article, and suppresses oxidation or pyrolysis of the soft segment can do.

For this purpose, the polylactic acid / acrylonitrile-butadiene-styrene copolymer alloy resin composition preferably has a weight average molecular weight of about 100 (in terms of the amount of monomers (for example, lactic acid or lactide) To about 3,000 ppmw, about 100 to 2,000 ppmw, about 500 to 1,500 ppmw, or about 1,000 to 1,500 ppmw.

When the content of the antioxidant is excessively low, the polylactic acid resin may be yellowed by oxidation of a softening component such as the soft segment, and the polylactic acid / acrylonitrile-butadiene-styrene copolymer alloy resin composition and molded article May be poor in appearance. On the other hand, when the content of the antioxidant is excessively high, the antioxidant may lower the polymerization rate of lactide or the like and hard segments containing the polylactic acid repeating units may not be properly formed. The mechanical properties And the like may be deteriorated.

When the antioxidant is contained in an optimized amount, for example, the antioxidant is added in an optimized amount at the time of polymerization for producing a polylactic acid resin, and the polylactic acid resin and the polylactic acid / acrylonitrile-butadiene-styrene copolymer In the case of obtaining the alloy resin composition, the conversion of polymerization and the degree of polymerization of the poly (lactic acid) resin can be improved to increase the productivity. Further, in a molding process which requires heating at 180 占 폚 or more to the polylactic acid / acrylonitrile-butadiene-styrene copolymer alloy resin composition, the polylactic acid / acrylonitrile-butadiene-styrene copolymer alloy resin Since the composition can exhibit excellent thermal stability, it is possible to inhibit the formation of monomers such as lactide or lactic acid or low molecular weight substances in the state of cyclic oligomers.

As a result, the molecular weight of the poly (lactic acid) resin is suppressed and the color change (yellowing) of the molded article is suppressed. As a result, not only excellent appearance but also greatly improved flexibility and excellent physical properties such as mechanical properties, heat resistance and blocking resistance It becomes possible to provide a molded article to be displayed.

As the antioxidant, at least one selected from the group consisting of a hindered phenol antioxidant, an amine antioxidant, a thio antioxidant and a phosphite antioxidant may be used, and other polyoxyalkylene / Various antioxidants known to be usable in the nitrile-butadiene-styrene copolymer alloy resin composition can be used.

However, since the polylactic acid / acrylonitrile-butadiene-styrene copolymer alloy resin composition can have an ester repeating unit, the polylactic acid / acrylonitrile-butadiene-styrene copolymer resin composition has a tendency of being oxidized or pyrolyzed during high- . Therefore, it is preferable to use the above-mentioned series of heat stabilizers, polymerization stabilizers or antioxidants as the antioxidant. Specific examples of such antioxidants include phosphoric acid type heat stabilizers such as phosphoric acid, trimethyl phosphate or triethyl phosphate; Butyl-p-cresol, octadecyl-3- (4-hydroxy-3,5-di-t- butylphenyl) propionate, tetrabis [methylene- Butyl-4-hydroxyphenyl) propionate] methane, 1,3,5-trimethyl-2,4,6-tris (3,5-di- 4-hydroxybenzylphosphite diethyl ester, 4,4'-butylidene-bis (3-methyl-6-t-butylphenol), 4, Such as 4'-thiobis (3-methyl-6-t-butylphenol) or bis [3,3-bis- (4'-hydroxy-3'- tert- butylphenyl) butanoic acid] Primary phenolic antioxidants; Amines such as phenyl-? -Naphthylamine, phenyl-? -Naphthylamine, N, N'-diphenyl-p-phenylenediamine or N, N'-di-? -Naphthyl- Secondary antioxidant; Such as thiourea such as diaryldisulfide, dilaurylthiopropionate, distearyl thiopropionate, mercaptobenzothiazole, or tetramethylthiuram disulfide tetrabis [methylene-3- (laurylthio) propionate] thio-based secondary antioxidants; (2,4-di-t-butylphenyl) pentaerythritol diphosphite or (1,1'-biphenyl) -4, triphenylphosphite, tris (nonylphenyl) phosphite, triisodecylphosphite, And a phosphite-based secondary antioxidant such as tetrakis [2,4-bis (1,1-dimethylethyl) phenyl] ester of 4'-diylbiposphonous acid. Among them, it is most preferable to use a combination of a phosphite-based antioxidant and another antioxidant.

In addition to the above-mentioned impact modifier and antioxidant, the polylactic acid / acrylonitrile-butadiene-styrene copolymer alloy resin composition may contain various well-known anti-hydrolysis inhibitors, nucleating agents, organic or inorganic fillers And further includes various additives such as a plasticizer, a chain extender, an ultraviolet stabilizer, a coloring inhibitor, a matting agent, a deodorant, a flame retardant, a lubricant, an antistatic agent, a releasing agent, an antioxidant, an ion exchanger, a coloring pigment, It is possible.

The above-mentioned moisture release is a reactive compound capable of reacting with a hydroxyl group or a carboxyl group which is a terminal component of polylactic acid, and can improve the hydrolysis resistance as well as the durability of the polylactic acid / acrylonitrile-butadiene-styrene copolymer resin composition . That is, the moisture release is applied to an ester resin such as polyester, polyamide or polyurethane to end-cap the end of the polymer chain to prevent hydrolysis of the resin composition by water or acid It plays a role. The moisture release may be a carbodiimide compound, for example, a modified phenyl carbodiimide, poly (tolylcarbodiimide), poly (4,4'-diphenylmethanecarbodiimide), poly (3,3 ' -Dimethyl-4,4'biphenylenecarbodiimide), poly (p-phenylenecarbodiimide), poly (m-phenylenecarbodiimide), poly (3,3'-dimethyl- Methane carbodiimide). The moisture release can be used in an amount of 5 parts by weight or less based on 100 parts by weight of the sum of the polylactic acid resin and the acrylonitrile-butadiene-styrene copolymer resin.

The nucleating agent may be contained in an amount of 10 parts by weight or less, preferably 5 parts by weight or less, based on 100 parts by weight of the total of the polylactic acid / acrylonitrile-butadiene-styrene copolymer alloy resin composition (including the nucleating agent) Within the above range, heat resistance and injection moldability are improved. The nucleating agent may be a sorbitol-based metal salt, a phosphate-based metal salt, a quinacridone, a calcium carboxylate, an amide-based organic compound, or the like, preferably a phosphate-based metal salt.

Examples of the plasticizer include phthalate ester plasticizers such as diethyl phthalate, dioctyl phthalate and dicyclohexyl phthalate; Aliphatic dibasic acid ester plasticizers such as di-n-butyl adipate, di-n-octyl adipate, di-n-butyl sebacate and di-2-ethylhexyl azelate; Phosphate ester plasticizers such as diphenyl-2-ethylhexyl phosphate and diphenyloctyl phosphate; Tributyl acetyl citrate, tri-2-ethylhexyl acetyl citrate, tributyl citrate, and other hydroxycarboxylic acid ester plasticizers; Fatty acid ester plasticizers such as methyl acetyl ricinoleate and stearic acid amide; Polyhydric alcohol ester plasticizers such as glycerin triacetate; Epoxidized soybean oil, epoxylated amami-oil fatty acid butyl ester, and epoxy-based stearyl epoxy stearate.

Examples of the colored pigments include inorganic pigments such as carbon black, titanium oxide, zinc oxide and iron oxide; Organic pigments such as cyanine pigments, phosphorus pigments, quinone pigments, lineron pigments, isoindolinone pigments, and thioindigo pigments.

On the other hand, when a molded article is manufactured using a poly (lactic acid / acrylonitrile-butadiene-styrene copolymer) alloy resin composition, it may contain inorganic or organic particles to improve the mold releasability and the like of the produced molded article. The inorganic or organic particles may be contained in an amount of 30 parts by weight or less, preferably 10 parts by weight or less, based on 100 parts by weight of the total of the polylactic acid / acrylonitrile-butadiene-styrene copolymer alloy resin composition. Examples of the inorganic or organic particles include silica, colloidal silica, alumina, alumina sol, talc, titanium dioxide, mica, calcium carbonate, polystyrene, polymethyl methacrylate, or silicone. The above silica, titanium dioxide or talc is not limited to whether or not the surface treatment is performed. However, when the surface treated titanium dioxide or talc is used, not only the whole property balance including rigidity and impact strength is excellent but also the specific gravity, heat resistance, The moldability is improved. Specifically, the surface treatment may be carried out by a chemical or physical method using a treating agent such as a silane coupling agent, a higher fatty acid, a metal salt of a fatty acid, an unsaturated fatty acid, an organic tinate, a resin acid or polyethylene glycol. The inorganic particles may have an average particle size of 1 to 30 탆, preferably 1 to 15 탆, and the heat resistance and rigidity are improved within the above range.

In addition, various additives known to be usable in a polylactic acid / acrylonitrile-butadiene-styrene copolymer alloy resin composition or a molded article thereof can be included, and specific types and methods of obtaining the same are obvious to those skilled in the art.

On the other hand, the poly-lactic acid / acrylonitrile-butadiene-styrene copolymer alloy resin composition may have a color-b value of less than 15 and preferably 10 or less in a chip state. Since the polylactic acid / acrylonitrile-butadiene-styrene copolymer alloy resin composition contains an antioxidant, the yellowing of the polylactic acid resin can be suppressed, so that it can exhibit a color-b value of less than 15. If the color-b value of the polylactic acid / acrylonitrile-butadiene-styrene copolymer alloy resin composition is 15 or more, the appearance of the molded article may become poor when used for molding, and the product value may be lowered.

Hereinafter, a method for producing polylactic acid contained in the polylactic acid / acrylonitrile-butadiene-styrene copolymer alloy resin composition of the present invention will be described in more detail.

&Lt; Preparation of polyolefin-based polyol structural units &gt;

First, a hydroxyl group is added to the terminal of a polymer (poly 1,2-butadiene or poly 1,3 -butadiene) obtained by conjugating a butadiene monomer, and a liquid polybutadiene having a molecular weight of 1,000 to 3,000 -terminated polybutadiene: HTPB) to obtain a (co) polymer having a polyolefin-based polyol constituent unit. This can be carried out according to a conventional method for producing a polyolefin-based polyol (co) polymer.

&Lt; Preparation of polyolefin-based polyol repeating unit A &

Then, the (co) polymer having the polyolefin-based polyol constituent unit, the polyfunctional isocyanate compound and the urethane reaction catalyst are charged in the reactor, heated and stirred to carry out the urethane reaction. By this reaction, two or more isocyanate groups of the isocyanate compound and a terminal hydroxyl group of the (co) polymer are bonded to form a urethane bond. As a result, a (co) polymer in which the polyolefin-based polyol constituent units have a polyurethane polyol repeating unit in a linear or branched connected form via the urethane bond can be formed. This is included as a soft segment of the above-described poly (lactic acid) resin. At this time, the polyurethane polyol (co) polymer is a polyol (co) polymer in which polyolefin-based polyol repeating units (O) are linearly or branched in the form of OUOUO or OU (-O) -OUO via a urethane bond And may be formed in a form having polyolefin-based polyol repeating units.

&Lt; Preparation of polyolefin-based polyol repeating unit B &

Further, the reactor is filled with the (co) polymer having the polyolefin-based polyol constituent unit, the lactic acid (D or L-lactic acid), the lactide (D or L-lactide) compound and the condensation reaction or the ring- To carry out a polyester reaction or a ring-opening polymerization reaction. By such a reaction, the lactic acid (D or L-lactic acid), the lactide (D or L-lactide) and the terminal hydroxyl group of the (co) polymer are bonded to form an ester bond. As a result, a (co) polymer in which the polyolefin-based polyol constituent units have a polyolefin-based polyol (O) and a polylactic acid resin repeat unit (L) in a linear or branched connected form via the ester bond can be formed. At this time, the polyolefin-based polyol and the poly (lactic acid) resin (co) polymer are obtained by a method in which polyolefin-based polyol repeating units (O) are linearly bonded in the form of LEOEL via ester bond (E) As shown in FIG.

Two or more isocyanate groups of an isocyanate compound and a terminal hydroxyl group of the (co) polymer are combined to form a urethane bond and are linearly or branched-bonded in the form of LEOELULEOEL so that the polylactic acid / acrylonitrile-butadiene- The final poly (lactic acid) resin contained in the copolymer alloy resin composition can be produced.

At this time, the polyolefin-based polyol repeating units obtained from the butadiene may be originated from biomass such as plant resources, and accordingly, the polyolefin-based polyol (co) polymer has an organic carbon content (% C _bio ) Can be a very high value of 70% by weight or more.

The urethane reaction can be carried out in the presence of a conventional tin catalyst, for example, stannous octoate, dibutyltin dilaurate, dioctyltin dilaurate and the like. In addition, the urethane reaction can be carried out under the reaction conditions for the production of a conventional polyurethane resin. For example, the isocyanate compound and the polyolefin-based polyol (co) polymer are added in a nitrogen atmosphere, the urethane reaction catalyst is added, and the reaction is carried out at a reaction temperature of 70 to 80 ° C for 1 to 5 hours to obtain a (co) polymer having polyolefin polyol repeating units Can be manufactured.

Then, when lactic acid (D or L-lactic acid) is subjected to condensation polymerization or lactide (D or L-lactide) is subjected to ring-opening polymerization in the presence of the (co) polymer having the polyolefin-based polyol repeating unit and the antioxidant, A polylactic acid / acrylonitrile-butadiene-styrene copolymer alloy resin composition containing a block copolymer (or a polylactic acid resin containing the same) and an antioxidant may be prepared. That is, when the polymerization reaction is carried out, the yellowing due to the oxidation of the soft segment and the like is suppressed by the antioxidant to form a polylactic acid repeating unit contained as a hard segment, and the polylactic acid resin is produced, The polyurethane polyol repeating unit may be bonded to the end of the repeating unit to form a block copolymer.

In addition, it is also possible to use a known polylactic acid copolymer prepared by preparing a prepolymer in which a polyolefin-based polyol and a lactide are bonded to each other and then chain-extending the prepolymers with a diisocyanate compound, And a polylactic acid / acrylonitrile-butadiene-styrene copolymer alloy resin composition containing the same can be formed.

Meanwhile, the lactide ring-opening polymerization reaction may be carried out in the presence of a metal catalyst including an alkaline earth metal, a rare earth metal, a transition metal, aluminum, germanium, tin or antimony. In particular, such metal catalysts may be in the form of carboxylates, alkoxides, halides, oxides or carbonates of these metals. Preferably, as the metal catalyst, tin octylate, titanium tetraisopropoxide or aluminum triisopropoxide may be used.

In addition, the polylactic acid repeating unit forming step such as the lactide ring-opening polymerization reaction may be continuously carried out in the same reactor in which the urethane reaction has proceeded. That is, a polyolefin-based polyol polymer and an isocyanate compound are subjected to a urethane reaction to form a polymer having polyolefin-based polyol repeating units, and then monomers such as lactide and a catalyst, etc., are continuously added to this reactor to form polylactic acid repeating units . As a result, while the polymer having polyolefin-based polyol repeating units functions as an initiator, the polylactic acid repeating units and the polylactic acid resin containing them can be continuously produced with high yield and high productivity. Likewise, when the polyolefin-based polyol is subjected to ring-opening polymerization with an initiator of lactide, and then isocyanate compound is continuously added in the same reactor to effect chain extension polymerization, the polylactic acid repeating unit and the polylactic acid resin containing the same are obtained at a high yield Can be continuously produced with good productivity.

The polylactic acid / acrylonitrile-butadiene-styrene copolymer alloy resin composition described above contains a block copolymer (polylactic acid resin) to which a specific hard segment and a soft segment are bonded, exhibits biodegradability of the polylactic acid resin Can also exhibit greater flexibility. Also, the soft segment for imparting flexibility can be minimized to be bleed out, and the degradation of moisture resistance, mechanical properties, heat resistance, transparency or haze characteristics of the molded article can be greatly reduced by the addition of such a soft segment.

In addition, since the poly (lactic acid) resin is produced so as to have a predetermined glass transition temperature and optionally a predetermined melting temperature, a molded article or the like obtained therefrom can exhibit optimized flexibility and strength as a packaging material, And the blocking resistance and the heat resistance are further improved. Accordingly, such a poly (lactic acid) resin and the poly (lactic acid / acrylonitrile-butadiene-styrene copolymer) resin composition containing the same can be suitably applied to packaging materials such as molded articles and the like.

The poly (lactic acid) / acrylonitrile-butadiene-styrene copolymer free resin composition containing these components can be used in combination with an antioxidant, It is possible to provide a molded article exhibiting various physical properties such as flexibility and mechanical properties which are remarkably improved while showing appearance and merchandise.

That is, the polylactic acid / acrylonitrile-butadiene-styrene copolymer alloy resin composition of the present invention contains the polyolefin-based polyol repeating unit as a soft segment, and thus the polylactic acid / acrylonitrile-butadiene- The flexibility of the molded article produced using the alloy resin composition can be greatly improved.

In addition, the moisture content in the whole resin is lowered by the resin component made of the polyolefin-based polyol of the non-polar soft segment relative to the hard segment, which is the hard segment, and moisture resistance can be greatly improved.

Best Mode for Carrying Out the Invention Hereinafter, the function and effect of the present invention will be described in more detail through specific examples of the present invention. It is to be understood, however, that these embodiments are merely illustrative of the invention and are not intended to limit the scope of the invention.

The raw materials used in the following Examples and Comparative Examples are as follows:

1. Polyolefin-based polyol repeating units and corresponding materials thereof

- HTPB 1.0: A liquid polybutadiene having a molecular weight of 1,000 obtained through hydrogenation reaction by adding a hydroxy group to the end of a polymer (poly 1,2-butadiene or poly 1,3 -butadiene) obtained by conjugating a butadiene monomer with a conjugated polymer -terminated polybutadiene: HTPB)

- HTPB 2.0: Liquid polybutadiene (HTPB) having a molecular weight of 2,000 obtained by hydrogenating a hydroxyl group at the end of a polymer (poly 1,2-butadiene or poly 1,3-butadiene) obtained by conjugating a butadiene monomer )

- HTPB 3.0: Liquid polybutadiene (HTPB) having a molecular weight of 3,000 obtained by hydrogenating a hydroxyl group at the terminal of a polymer (poly 1,2-butadiene or poly 1,3-butadiene) obtained by conjugating a butadiene monomer )

- HTPB 5.0: Liquid polybutadiene (HTPB) having a molecular weight of 5,000 obtained by hydrogenating a hydroxyl group at the terminal of a polymer (poly 1,2-butadiene or poly 1,3-butadiene) obtained by conjugating a butadiene monomer )

- PEG 8.0: polyethylene glycol; Number average molecular weight 8,000

- PBSA 11.0: aliphatic polyester polyols made from 1,4-butanediol and condensates of succinic acid and adipic acid; Number average molecular weight 11,000

2. Diisocyanate compound and trifunctional or higher isocyanate

- HDI: hexamethylene diisocyanate

- TDI: 2,4- or 2,6-tolylene diisocyanate (toluene diisocyanate: TDI)

- D-L75: Bayer desmodur L75 (trimethylol propane + 3 toluene diisocyanate)

3. Lactide monomers

-L-lactide or D-lactide: manufactured by purac, optical purity not less than 99.5%

Monomers consisting only of organic carbon of biomass origin

4. Antioxidants, etc.

- TNPP: Tris (nonylphenyl) phosphite

- U626: bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite

- S412: tetrakis [methane-3- (laurylthio) propionate] methane

- PEPQ: Tetrakis [2,4-bis (1,1-dimethylethyl) phenyl] ester (1,1'-biphenyl) -4,4'-

- I-1076: octadecyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate

O3: bis [3,3-bis- (4'-hydroxy-3'-tert-butylphenyl) butanoic acid] glycol ester

5. Acrylonitrile-butadiene-styrene copolymer resin, etc.

ABS 745: 40% by weight of an acrylonitrile-butadiene-styrene copolymer (ABS) consisting of 20% by weight of acrylonitrile, 25% by weight of butadiene and 55% by weight of styrene and 40% by weight of styrene- acrylonitrile copolymer (SAN) 10 kg / 10 min (220 캜, 10 kg), thermal deformation temperature 84 캜, impact strength (6.4 mm, 23 캜) 35 kgf-cm / cm

6. Impact reinforcement

- G1701: styrene / ethylene / propylene block copolymer, KRAPTON, hardness 72 HD (Shore A, 30 s), 37 wt% styrene

- MB838A: methyl methacrylate-butadiene-styrene (MBS) block copolymer, LG Chemical Co., Ltd., hardness 71 HD (Shore A, 30s)

- Biostrength 150: Acrylic core-shell impact modifier, ARKEMA

7. Inorganic fillers and nucleating agents

- SP-3000: Talc, Dae Won Chemical Co., Ltd., average particle size 2.5 탆, specific gravity 0.32 g / cm ²

- EMforce ™ Bio: CaC0 ₂ , Special Mineral, average particle size 1.0 μm, average aspect ratio 5.4

- TF-1: N, N ', N "-tricyclohexyl-1,3,5-benzenetricarboxamide, NJC

- NA-11: 2,2'-methylenebis (4,6-di-tert-butylphenol) sodium phosphate, Asahi Denka

8. Moisture Release and Chain Extender

- BioAdimide 100: carbodiimide polymer, Rhein Chemie

9. Commercialization etc.

- AX8840: ethylene-maleic anhydride graft-glycidyl methacrylate copolymer, ARKEMA company, graft ratio 8.0%

- PH-200: propylene-maleic anhydride graft copolymer, Honam Petrochemical Co., Ltd., graft rate 3.9%

Production Examples 1 to 6: Preparation of Poly (lactic acid) Resins A to F

Components and contents of reactants as shown in the following Table 1 were charged together with the catalyst in an 8 L reactor equipped with a nitrogen gas inlet tube, a stirrer, a catalyst inlet, an outlet condenser and a vacuum system. As the catalyst, 130 ppmw of dibutyltin dilaurate relative to the total reactant content was used. The urethane reaction was conducted under a nitrogen stream at 70 ° C for 2 hours, and 4 kg of L- (or D-) lactide was added thereto, followed by nitrogen flushing five times.

Then, the temperature was raised to 150 ° C to completely dissolve the L- (or D-) lactide, and the catalyst, tin 2-ethylhexylate, was diluted with 500 ml of toluene to 120 ppmw relative to the total reactant content, . The reaction was carried out at 185 ° C under 1 kg of nitrogen pressure for 2 hours, 200 ppmw of phosphoric acid was added to the catalyst inlet, and the mixture was mixed for 15 minutes to inactivate the residual catalyst. The unreacted L- (or D-) lactide (about 5 wt% of the initial charge) was then removed through a vacuum reaction until a 0.5 torr was reached. The molecular weight characteristics, Tg, Tm,% C _bio, etc. of the obtained resin were measured and shown in Table 1.

Production Example 7: Preparation of poly (lactic acid resin G)

To an 8 L reactor equipped with a nitrogen gas inlet, a stirrer, a catalyst inlet, an outlet condenser and a vacuum system, 865 g of HTPB 2.0, 3.9 kg of L-lactide and 0.1 kg of D- And nitrogen flushing was performed five times. The temperature was raised to 150 ° C to completely dissolve the lactide, and 120 ppmw of tin 2-ethylhexylate as a catalyst was diluted with 500 ml of toluene through a catalyst inlet and added to the reaction vessel. Subsequently, the reaction was carried out at 185 ° C under a pressure of 1 kg of nitrogen for 2 hours, 200 ppmw of phosphoric acid was added to the catalyst inlet, and the mixture was mixed for 15 minutes to inactivate the residual catalyst. Unreacted L-lactide (about 5 parts by weight of the initial charge) was removed through a vacuum reaction until 0.5 torr was reached. Subsequently, 120 ppmw of HDI and catalyst dibutyltin dilaurate as shown in Table 1 below were diluted with 500 ml of toluene through a catalyst inlet and added to the reaction vessel. The reaction was carried out in a nitrogen atmosphere at 190 DEG C for 1 hour, and the molecular weight characteristics, Tg, Tm and% C _bio, etc. of the obtained resin were measured and are shown in Table 1.

Production Example 8: Production of poly (lactic acid resin) H

885 g of HTPB2.0, 3.8 kg of L-lactide and 0.2 kg of D-lactide were used as shown in the following Table 1, and then HDI and D-L75 Was prepared in the same manner as in Production Example 7, The molecular weight characteristics, Tg, Tm,% C _bio, etc. of the obtained resin were measured and shown in Table 1.

Production Example 9: Preparation of poly (lactic acid resin I)

The polyol and 4 kg of L-lactide were charged into an 8 L reactor equipped with a nitrogen gas inlet tube, a stirrer, a catalyst inlet, an outlet condenser and a vacuum system, and subjected to nitrogen flushing five times. The temperature was raised to 150 ° C to completely dissolve the L-lactide, and 120 ppmw of catalyst tin 2-ethylhexylate was diluted with 500 ml of toluene through the catalyst inlet and added to the reaction vessel. Subsequently, the reaction was carried out at 185 ° C under a pressure of 1 kg of nitrogen for 2 hours, 200 ppmw of phosphoric acid was added to the catalyst inlet, and the mixture was mixed for 15 minutes to inactivate the residual catalyst. Unreacted L-lactide was removed through vacuum reaction until 0.5 torr was reached. The molecular weight characteristics, Tg, Tm,% C _bio, etc. of the obtained resin were measured and shown in Table 1.

Production Example 10: Production of poly (lactic acid resin J)

Except that 378.8 g of PPDO2.4 (poly (1,3-propanediol), number average molecular weight 2,400) was added instead of the polyol as shown in Table 1 below. The molecular weight characteristics, Tg, Tm,% C _bio, etc. of the obtained resin were measured and shown in Table 1.

Production Example 11: Production of poly lactic acid resin K

Was prepared in the same manner as in Production Example 9, except that 6 g of 1-dodecanol was added instead of the polyol as shown in Table 1 below. The molecular weight characteristics, Tg, Tm,% C _bio, etc. of the obtained resin were measured and shown in Table 1.

Production Example 12: Preparation of poly lactic acid resin L

A PBSA polyol (polyester polyol) and HDI were charged into an 8 L reactor equipped with a nitrogen gas introducing tube, a stirrer, a catalyst inlet, an outlet condenser and a vacuum system as shown in Table 1 below and nitrogen flushing five times. As the catalyst, 130 ppmw of dibutyltin dilaurate relative to the total reactant content was used. The urethane reaction was carried out for 2 hours at a reactor temperature of 190 占 폚 under a nitrogen stream, 4 kg of L-lactide was introduced, L-lactide was completely dissolved at 190 占 폚 in a nitrogen atmosphere and the total reactant content Concentration addition catalyst 120 ppmw of tin 2-ethylhexylate and 1,000 ppmw of dibutyltin dilaurate as an ester and / or esteramide exchange catalyst were diluted with 500 ml of toluene and added to the reaction vessel. The reaction was carried out at 190 DEG C under 1 kg of nitrogen pressure for 2 hours, 200 ppmw of phosphoric acid was added to the catalyst inlet and mixed for 15 minutes to inactivate the residual catalyst. The unreacted L-lactide (about 5 wt.% Of the initial charge) was then removed through a vacuum reaction until 0.5 torr was reached. The molecular weight characteristics, Tg, Tm,% C _bio, etc. of the obtained resin were measured and shown in Table 1.

Examples 1 to 8 and Comparative Examples 1 to 8: Production of molded articles

The polylactic acid resins prepared in Preparation Examples 1 to 12 were respectively dried under reduced pressure at 80 ° C for 6 hours under a vacuum of 1 torr, and then the acrylonitrile-butadiene-styrene copolymer resin and its Were mixed using a super mixer and extruded at an extrusion temperature of 220 to 250 mm in a 19 mm diameter twin screw extruder (one of various compounding machines such as a uniaxial extruder, a roll mill, a kneader or a Banbury mixer could be used) Lt; 0 &gt; C. The cooled strands through a water bath were prepared in the form of pellets using a pelletizer. This was dried in a dehumidifying dryer or a hot-air dryer at 80 ° C for 4 hours or more, and injection-processed to prepare a specimen. The evaluation results of the obtained molded article are shown together in Table 2 or 3

Experimental Example

(1) NCO / OH: reaction of terminal hydroxyl group of isocyanate group / polyether polyol repeat unit (or (co) polymer) of "diisocyanate compound (for example, hexamethylene diisocyanate) for formation of polyolefin- Molar ratio.

(2) OHV (KOH mg / g): The polyolefin-based polyol repeating unit (or (co) polymer) was dissolved in dichloromethane and acetylated, and acetic acid produced by hydrolysis thereof was titrated with a 0.1N KOH methanol solution . This corresponds to the number of hydroxyl groups present at the ends of the polyolefin-based polyol repeating unit (or (co) polymer).

(3) Mw and Mn (g / mol) and Molecular Weight Distribution (Mw / Mn): The poly lactic acid resin was dissolved in chloroform at a concentration of 0.25% by weight and subjected to gel permeation chromatography (Viscotek TDA 305, column: Shodex LF804 × 2 ea), and the weight average molecular weight (Mw) and the number average molecular weight (Mn) were respectively calculated as polystyrene as a standard material. Molecular weight distribution values were calculated from the Mw and Mn thus calculated.

(4) Tg (glass transition temperature, 占 폚): Measured by heating the sample at 10 占 폚 / min after melting and quenching the sample using a differential scanning calorimeter (TA Instruments). The midline value of the tangent line and the baseline near the endothermic curve was defined as Tg.

(5) Tm (melting temperature, 占 폚): Using a differential scanning calorimeter (manufactured by TA Instruments), the sample was subjected to melt quenching and then heated to 10 占 폚 / min. The maximum value of the melting endothermic peak of the crystal was defined as Tm.

(6) Residual monomer (lactide) content (% by weight): 0.1 g of the resin was dissolved in 4 ml of chloroform, and 10 ml of hexane was added thereto.

(7) Content of polyolefin-based polyol repeating units (% by weight): The content of the polyolefin-based polyol repeating units contained in each produced poly (lactic acid) resin was quantified using a 600 Mhz nuclear magnetic resonance (NMR) spectrometer.

(8) Chip color-b: The value of the resin chip was determined using a color difference meter (CR-410, manufactured by Konica Minolta Sensing), and the average value of the test was measured five times in total.

(9) Organic carbon content of biomass origin (% C _bio ): The content of organic matter originating from biomass is measured from the content of biomass originating material by radioactive carbon concentration (Percent Modern; C14) according to ASTM D6866 Respectively.

(10) Extrusion state: Extrusion of a polylactic acid polylactic acid / acrylonitrile-butadiene-styrene copolymer alloy resin at a temperature of 220 to 250 DEG C in a 30 mm diameter twin screw extruder equipped with a hole die Extruded into a strand at a temperature, and then solidified in a cooling water bath at 20 ° C. At this time, the melt viscosity and the uniformity of the melt of the strand-form discharge were grasped visually and the state of melt viscosity (extrusion state) was evaluated according to the following criteria.

◎: Good compatibility between the two resins, uniformity of melt viscosity and generation of strand are good and not broken

○: There is a slight lack of compatibility between the two resins, and the uniformity of the melt viscosity is also somewhat low, so strand formation is difficult, but the formation itself is possible and breakage occurs

X: The compatibility between the two resins was so insufficient and the melt viscosity and uniformity were also poor, resulting in die swelling, which could not be generated as the strands were cut off.

(11) MI (melt index): The average value of the test was measured three times in total at a temperature of 220 DEG C and a load of 2.16 kgf according to ASTM D1238.

(12) Compatibility: In a 30 mm diameter twin screw extruder equipped with a hole die, a polylactic acid resin polylactic acid / acrylonitrile-butadiene-styrene copolymer alloy resin was extruded at 220 to 250 ° C Extruded at a temperature and solidified in a cooling water bath at 20 ° C to obtain a strand specimen. The strand specimen was immersed in and fractured in liquid nitrogen. The cut surface was observed with a scanning electron microscope (SEM) . &Lt; / RTI &gt;

⊚: Good dispersion state between two resins and finely dispersed resin particle diameter of not more than 0.2 탆

?: Good dispersion state between two resins and a finely dispersed resin particle diameter of 1.0 占 퐉 or less,

X: poor dispersion state between two resins and finely dispersed resin particle diameter of 1.0 占 퐉 or more;

(13) Appearance characteristics: Appearance was visually judged, and the flow mark, weld line and gloss drop caused by insufficient flow of resin melt were judged.

◎: Good melt viscosity, no flow mark, weld line, excellent gloss

○: The melt viscosity is slightly high, so there is no flow mark or weld line, but the gloss is poor

X: very high melt viscosity, resulting in flow mark, weld line and gloss dropping

(14) Initial Tensile Strength (kgf / cm 2): According to ASTM D638, the specimens were matured for 24 hours in an atmosphere at a temperature of 20 ° C and a humidity of 65% RH and subjected to a total of five tests (INSTRON) And the average value was expressed as a result.

(15) Elongation (%): The elongation at break of the specimen under the same condition as the initial tensile strength of (14) was measured, and the average value of the test was measured five times in total.

(16) Impact strength (kgf-cm / cm): A test specimen was prepared in accordance with ASTM D 256, and the impact strength value was measured using an Izod impactor.

(17) Bending strength (kgf / cm2) and bending elastic modulus (kgf / cm2): A test piece was prepared in accordance with ASTM D790 and the average value of the test was measured five times using UTM (INSTRON) universal testing machine. Respectively.

(18) Heat resistance (占 폚): A test piece for measurement was prepared in accordance with ASTM D648, and heat resistance was measured using a universal testing machine.

i) High temperature mold: High temperature mold at 110 ℃ was used for injection, cooling time was 30 seconds or less

ii) Cold mold: Normal temperature mold was used for injection and cooling time was 30 seconds or less

(19) Bleed-out: The surface of the molded article was observed, and the extent to which the low molecular weight plasticizer component was absorbed to the surface of the molded article by tactile sensation was evaluated according to the following criteria using an A4 size film sample.

◎: No generation of suction

○: Suction occurs but not severe

×: Severe draft

(20) Humidity tensile strength retention (%): A film sample having a length of 150 mm and a width of 10 mm was subjected to initial tensile strength change after 30 days in an atmosphere at a temperature of 40 DEG C and a humidity of 90% RH for 30 days.

(21) Odor generation: compounding Each composition extruded and kneaded was checked whether or not a volatile odor was formed in the discharged product.

◎: Occurrence of odor

X: No odor occurred.

(22) Total Volatile Organic Compounds (TVOC): HeadSpace-GC / MS-Material Analysis

1) Take 2 g of the sample and seal it in a sealed vial. After HS-GC / MS analysis

2) STD: 50 μl of each of toluene 250, 500, and 1000 ppm was sealed in a vial, and HS-GC / MS analysis

3) HS-GC / MS

- HS: After heating at 180 ℃ (30 min), upper gas analysis

Column DB-5 (60 m x 0.32 mm x 1.0 mu m)

-80 ° C (5 min) -10 ° C / min-320 ° C (16 min), inject 280 ° C, 1:30 split

(23) Chemical Resistance: 10 ml of gasoline and perfume solvent were placed in 20 ml vials, and 10 mm × 30 mm × 2 mm of each specimen was observed.

◎: no whitening or swelling occurs

○: Swelling does not occur, but whitening occurs

×: Whiteing and swelling occur

Referring to Table 2, Examples 1 to 5 and Examples 7 and 8 show that the content of the softening component (polyolefin-based polyol repeating unit) in the poly (lactic acid resin) is 5 to 35% by weight, the color b value is low, Of an antioxidant and having a weight average molecular weight of 100,000 to 400,000, a molecular weight distribution of 1.60 to 3.0, a Tg of 20 to 60 占 폚 and a Tm of 145 to 178 占 폚, and a polylactic acid / acrylonitrile-butadiene -Styrene copolymer solid resin composition. In Example 6, the polylactic acid resin (resin F) corresponding to the polylactic acid resin contained in the polylactic acid / acrylonitrile-butadiene-styrene copolymer alloy resin composition of the present invention and the general polylactic acid resin (resin K Acrylonitrile-butadiene-styrene copolymer alloy resin composition containing a polylactic acid / acrylonitrile-butadiene-styrene copolymer resin.

All of the injection molded articles of Examples 1 to 8 have excellent mechanical properties such as an initial tensile strength of 300 kgf / cm 2 or more and an impact strength of 15 kgf-cm / cm or more, as well as high temperature mold HDT Heat resistance. Also, it was confirmed that the tensile strength retention after immersion in the atmosphere of 40 DEG C and humidity of 90% RH was excellent at 80% or more after 30 days, TVOC content was 200 ppm or less without use of styrene or acrylic compatibilizer and plasticizer, It was possible to effectively reduce the amount of total volatile organic compounds harmful to the human body. Further, the biomass content of the resin is 25% or more, which is an environmentally friendly material.

On the other hand, the injection molded article of Comparative Example 1, which was made of polylactic acid / acrylonitrile-butadiene-styrene copolymer alloy resin containing polylactic acid resin A containing a polyolefin-based polyol as a soft segment, However, the biodegradable content was less than 25%, which did not meet the global environmentally friendly plastic standards. The extrusion kneaded resin of Comparative Example 2, which was produced from a polylactic acid / acrylonitrile-butadiene-styrene copolymer alloy resin composition containing a general polylactic acid resin K, was a mixture of a polylactic acid resin and acrylonitrile-butadiene- The extrusion state was poor such as occurrence of die swelling in the extrusion kneaded soot, the tensile strength was less than 200 kgf / cm 2, the impact strength was 5 kgf-cm / cm &lt; / RTI &gt; and poor moisture resistance, making it difficult to use as an injection molded article. In addition, in the case of the injection molded articles of Comparative Examples 3 and 4 prepared from the polylactic acid / acrylonitrile-butadiene-styrene copolymer alloy resin composition using the polylactic acid resin K and the compatibilizing agent together, Although the extrusion state was good due to the introduction of a compatibilizing agent, compatibility between the two resins was not sufficient, and the mechanical properties, moisture resistance and heat resistance of the final injection molded article were poor. In addition, odor problems and bleed-out problems caused by the use of compatibilizers were serious.

In Comparative Example 5, poly (1,3-propanediol) having a number average molecular weight of 2,400 as a plasticizer component was not contained in the soft segment polyolefin-based polyol repeating unit in the poly (lactic acid) resin, The injection molded product of Comparative Example 5 had insufficient degree of dispersion of the plasticizer component in the resin, so that the haze of the melt during extrusion kneading was high, the extruded state and appearance characteristics were poor, and after the lapse of time A phenomenon that the plasticizer component bleed out from the injection molded article was found, and the moisture resistance and TVOC (total volatile organic compound) characteristics were poor.

Further, in Comparative Examples 6 and 7 prepared from a polylactic acid / acrylonitrile-butadiene-styrene copolymer alloy resin composition using polylactic acid resin I and polylactic acid J each containing polyether-based urethane polyol as a soft segment Even in the case of injection molded articles, the difference in melting point between the two resins and the lack of compatibility is too large to be used as an injection molded article due to a poor extrusion state such as occurrence of die swelling in extrusion kneaded soot.

In addition, the injection-molded article of Comparative Example 8 had a polyester polyol repeating unit introduced therein and a broad molecular weight distribution Acrylonitrile-butadiene-styrene copolymer alloy resin containing a poly (lactic acid) resin. The injection molded product of Comparative Example 8 exhibited relatively excellent bleed-out characteristics and TVOC characteristics as the polyurethane as a softening component was randomly introduced into a small segment size. However, since the polylactic acid repeating unit was introduced into a relatively small segment size , Low Tm, and the like, and all of the mechanical strengths were poor due to compatibility problems. In addition, it has been confirmed that the extrusion kneaded product is uneven due to the low miscibility of the polyester polyol and the polylactic acid used for forming the softening component, resulting in poor extruded state of the molded article and deterioration of the mechanical properties, and the moisture resistance is very poor .

On the other hand, the morphologies of the pellets prepared in Examples 1 to 3 were observed using an electron microscope (SEM), and the results are shown in Figs. 1 to 3, respectively. In the case of Figs. 1 to 3, the distinction between the polylactic acid resin and the acrylonitrile-butadiene-styrene copolymer resin did not appear clearly regardless of the ratio of the polylactic acid resin and the acrylonitrile-butadiene-styrene copolymer resin Able to know. This means that the compatibility between the two resins is increased without the use of a special compatibilizer, which shows that the balance of physical properties of flexural modulus and impact strength is improved.

In the polylactic acid resin / acrylonitrile-butadiene-styrene copolymer alloy resin composition, the polylactic acid resin is contained in the acrylonitrile-butadiene-styrene copolymer resin or in the acrylonitrile-butadiene- It is understood that the styrene copolymer resin increases the dispersibility in the polylactic acid resin, thereby improving the impact resistance, the crystallization speed and the heat resistance, which are weak points of the polylactic acid resin, thereby achieving a balance of the overall physical properties of the resin composition.

Claims (16)

Acrylonitrile-butadiene-styrene copolymer block copolymer composition comprising (1) 30 to 90 parts by weight of a polylactic acid resin and (2) 70 to 10 parts by weight of an acrylonitrile-butadiene-styrene copolymer resin as,
The polylactic acid resin (1) comprises a hard segment comprising a polylactic acid repeating unit represented by the following formula (1), and a polyolefin-based polyol constituent unit represented by the following formula (2) in a linear or branched Based polyol repeat units,
A polylactic acid / acrylonitrile-butadiene-styrene copolymer alloy resin composition having an organic carbon content (% C _bio ) of biomass origin defined by the following formula (1): 60 wt%
[Chemical Formula 1]

(2)

[Equation 1]
% C = _Bio (poly ¹⁴ C isotope ratio by weight of the ¹² C isotope of carbon atoms of the lactic acid resin) / ⁽¹⁴ C isotope ratio by weight of the ^bio-12 C isotope of carbon atoms of the mass origin standard)
In the general formulas (1) and (2), n is an integer of 700 to 5,000 and m + 1 is an integer of 5 to 200.
The method according to claim 1,
A polylactic acid / acrylonitrile-butadiene-styrene copolymer resin further comprising 0.1 to 20 parts by weight of an impact modifier based on 100 parts by weight of the total of the polylactic acid resin (1) and the acrylonitrile-butadiene-styrene copolymer resin (2) Styrene copolymer alloy resin composition.
The method according to claim 1,
The polylactic acid / acrylonitrile-butadiene-styrene copolymer alloy resin composition according to claim 1, wherein the content of the ¹⁴ C isotopes in carbon atoms of the polylactic acid resin is 7.2 × 10 ^-11 wt% to 1.2 × 10 ^-10 wt%.
The method according to claim 1,
Wherein the soft segment contains organic carbon of biomass origin as defined in Equation (1) in a content (% C _bio ) of 70 wt% or more.
The method according to claim 1,
Wherein the poly (lactic acid) resin has a number average molecular weight of 50,000 to 200,000 and a weight average molecular weight of 100,000 to 400,000.
The method according to claim 1,
Wherein the poly (lactic acid) resin has a glass transition temperature (Tg) of 20 to 55 占 폚 and a melting temperature (Tm) of 145 to 178 占 폚.
The method according to claim 1,
Wherein the urethane bond is formed by a reaction between a hydroxyl group at the end of the polyolefin-based polyol structural unit or a prepolymer obtained by addition polymerization of a lactide to the hydroxyl group at the end of the polyolefin-based polyol structural unit, and a polyisocyanate compound formed by reaction of a diisocyanate or an isocyanate compound having two or more functional groups / Acrylonitrile-butadiene-styrene copolymer alloy resin composition.
The method according to claim 1,
Wherein the polylactic acid resin is a block copolymer in which the terminal carboxyl group of the polylactic acid repeating unit contained in the hard segment is bonded to the terminal hydroxy group of the polyolefin polyol constituent unit contained in the soft segment by ester bonding,
Wherein the block copolymer comprises a linear or branched block copolymer linked via a urethane bond. 2. The polylactic acid / acrylonitrile-butadiene-styrene copolymer block copolymer according to claim 1,
9. The method of claim 8,
Wherein the polylactic acid resin further comprises a polylactic acid homopolymer not bonded to the polyolefin-based polyol repeating unit. 2. The polylactic acid / acrylonitrile-butadiene-styrene copolymer resin composition according to claim 1,
The method according to claim 1,
Wherein the polymer of the polyolefin-based polyol repeating unit has a number average molecular weight of 1,000 to 100,000.
9. The method of claim 8,
Wherein the reaction molar ratio of the hydroxyl group at the end of the polyolefin-based polyol structural unit to the diisocyanate or the isocyanate group of the isocyanate compound having two or more functional groups is 1: 0.50 to 1: 0.99, and the polyol / Composition.
The method according to claim 1,
Wherein the polylactic acid resin is a polylactic acid / acrylonitrile-butadiene-styrene copolymer alloy resin composition comprising 65 to 95 parts by weight of the hard segments and 5 to 35 parts by weight of soft segments relative to 100 parts by weight of the polylactic acid resin .
The method according to claim 1,
Wherein the acrylonitrile-butadiene-styrene copolymer resin is a polylactic acid / acrylonitrile-butadiene-styrene copolymer which is a copolymer comprising 10 to 30% by weight of acrylonitrile, 10 to 30% by weight of butadiene, and 40 to 70% Styrene copolymer alloy resin composition.
The method according to claim 1,
Wherein the acrylonitrile-butadiene-styrene copolymer resin is a polylactic acid resin comprising 30 to 70 parts by weight of styrene-acrylonitrile copolymer (SAN) based on 100 parts by weight of an acrylonitrile-butadiene- / Acrylonitrile-butadiene-styrene copolymer alloy resin composition.
The method according to claim 1,
Acrylonitrile-butadiene-styrene copolymer alloy resin composition exhibiting a color-b value of less than 10.
The method according to claim 1,
Wherein the polylactic acid / acrylonitrile-butadiene-styrene copolymer resin composition has a monomer content of less than 1% by weight based on the total weight of the polylactic acid resin.

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