WO2015060689A1 - Composition de résine d'alliage de poly(acide lactique)-polyamide - Google Patents

Composition de résine d'alliage de poly(acide lactique)-polyamide Download PDF

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Publication number
WO2015060689A1
WO2015060689A1 PCT/KR2014/010076 KR2014010076W WO2015060689A1 WO 2015060689 A1 WO2015060689 A1 WO 2015060689A1 KR 2014010076 W KR2014010076 W KR 2014010076W WO 2015060689 A1 WO2015060689 A1 WO 2015060689A1
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Prior art keywords
polylactic acid
resin
polyamide
resin composition
weight
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PCT/KR2014/010076
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English (en)
Korean (ko)
Inventor
정재일
유영만
이계윤
전성완
김민영
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에스케이케미칼주식회사
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Publication of WO2015060689A1 publication Critical patent/WO2015060689A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
    • C08G63/08—Lactones or lactides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/44—Polyester-amides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/12—Polyester-amides

Definitions

  • the present invention relates to a polylactic acid-polyamide alloy resin composition, and more specifically, exhibits improved impact strength as well as heat resistance, moisture resistance, mechanical properties, and injection processability.
  • the present invention relates to an alloy resin composition comprising a polylactic acid resin and a polyamide resin having excellent environmental properties and can be usefully used as a molded article material.
  • Crude oil-based resins such as polyylene terephthalate (PET), nylon (nylon), polyolefin (polyolefin) or soft polyvinyl chloride (PVC) are still widely used as materials for various applications such as packaging materials.
  • PET polyylene terephthalate
  • nylon nylon
  • polyolefin polyolefin
  • PVC soft polyvinyl chloride
  • such crude oil-based resins do not have biodegradability and thus cause environmental pollution such as discharging large amounts of carbon dioxide, which is a global warming gas, when disposed.
  • biomass-based resins typically polylactic acid resins
  • polylactic acid resins do not have sufficient heat resistance, moisture resistance, or mechanical properties, compared to crude oil-based resins, it is true that the polylactic acid resins have limitations in applications or applications.
  • polylactic acid resins or other general purpose resins and / or alloyed compositions of engineering plastics are used.
  • a molded article including polylactic acid resin is obtained using this alloy composition, in most cases, there is a limit in improving heat resistance and mechanical properties due to compatibility problems between the two resins. to be.
  • polylactic acid resins are generally very poor in moisture resistance, which is mainly caused by the hydrolysis reaction with water in the resin, and as a result, part of the polymer is decomposed into lactic acid, monomer or oligomer. And molecular weight fall occurs.
  • the resulting lactic acid and monomer organic oligomers may volatilize during the molding process of the resin, causing contamination and corrosion of the mechanical equipment and causing quality problems of the molded product.
  • a relief enemy ' it is twibal when the residual heritage, monomer and up meoga sheet extrusion resin and sikigido generating a thickness deviation of the sheet, even after the diameter of the injection molded articles right made according to the user environment, Sustained hydrolysis may occur, resulting in lower mechanical properties.
  • the water absorption is very easy, so when the water is passed through the extruder to work in a water bath (cooling), or stored in the pellet state when the storage of these compounding products increases, Injecting a molded article by using the resin may cause problems such as poor appearance or deterioration of physical properties such as silver streak due to moisture in the resin.
  • the object of the present invention is not only to exhibit improved impact resistance, but also excellent in various physical properties such as moisture resistance, mechanical properties, transparency, heat resistance, blocking resistance, molding processability, and the like. It is to provide a polylactic acid-polyamide alloy resin composition having characteristics.
  • the present invention is a polylactic acid-polyamide alloy resin composition
  • the polylactic acid resin may include a hard segment including a polylactic acid repeating unit represented by Chemical Formula 1, and a polyolefin-based polyol repeating unit in which polyolefm polyol structural units represented by Chemical Formula 2 are connected to a urethane bond or an ester bond or branched.
  • a polylactic acid-polyamide alloy resin composition comprising a soft segment ratio, wherein the organic carbon anti-oil (% C bio) of biomass origin, defined by Equation 1, is 60% or more:
  • % c Bio ( 14 c isotope weight ratio to 12 c isotopes in carbon atoms of the polylactic acid resin) I ( w c isotope weight ratio to 12 c isotopes in carbon atoms of the biomass-derived material) X 100
  • n is an integer of 700 to 5,000
  • m + 1 is an integer of 5 to 200.
  • the polylactic acid-polyamide alloy resin wool according to the present invention not only exhibits improved impact resistance, but also has excellent physical properties such as heat resistance, moisture resistance, mechanical cryogenicity and injection processability, and thus can be usefully used as a molded article material. Due to its environmental characteristics, it can greatly contribute to the prevention of environmental pollution. .
  • Figure 4 is an electron micrograph (SEM) of the pellet prepared in Comparative Example 4. Detailed description
  • the polylactic acid-polyamide alloy resin composition according to the present invention comprises (A) 30 to 90 parts by weight of a polylactic acid resin and (B) 10 to 70 parts by weight of a polyamide resin, wherein the polylactic acid resin (A) is A hard segment including a pulley lactic acid repeating unit of Formula 1, and a polyolefm polyol repeating unit in which the polyolefm-based polyol structural units of the following Chemical Formula 2 are linearly or branched connected through a urethane bond or an ester bond
  • An organic carbon content rate (% Cbio) of biomass origin defined by Equation 1, comprising:
  • % c bi s (polylactic acid resin ⁇
  • n is an integer of 700 to 5,000
  • m + 1 is an integer of 5 to 200.
  • the polylactic acid resin included in the polylactic acid-polyamide alloy resin composition according to the present invention basically includes a polylactic acid repeating unit represented by Chemical Formula 1 as a hard segment.
  • Such polylactic acid resins may exhibit biodegradable and eco-friendly characteristics peculiar to biomass-based resins by including a pulley lactic acid repeating unit as a hard segment.
  • the experimental results of the present inventors by including the polyolefin-based polyol repeating unit as a soft segment, not only shows a greatly improved flexibility using the polylactic acid resin, but also exhibits excellent transparency and low haze value. It has been found that molded parts can be produced.
  • the soft segment is introduced into the polylactic acid resin in a combined form with the hard segment, there is a possibility that the soft segment for improved flexibility is less bleed out or exhibits low stability, and the polylactic acid resin includes the polylactic acid resin.
  • the polylactic acid resin may exhibit the above-described effects without increasing the content of the soft segment for improved flexibility, such as hard derived from a relatively high content of biomass-based resins, such as polylactic acid resins. It may include a segment.
  • the polylactic acid resin contains a non-polar soft segment, it has excellent moisture resistance as compared to ordinary polylactic acid resins.
  • the polylactic acid resin included in the polylactic acid-pullyamide alloy resin composition may have an organic carbon content (% C bio) of about 60% or more, about 70% or more, and about 80% of the biomass origin defined by Equation 1 above. Or at least about 85%, at least about 90%, or at least about 95%.
  • % C bio organic carbon content
  • the polylactic acid resin included in the polylactic acid-polyamide alloy resin composition of the present invention such as Iodine, it is excellent to include polyester-based repeating units other than polyolefin-based polyol repeating units as soft segments.
  • the method for accumulating the organic carbon content of the biomass origin (% C bio) according to Equation 1 may be, for example, according to the method described in the ASTM D6866 standard.
  • the specific meaning of the organic carbon-containing alcohol (% C bio) can be found more specifically as follows.
  • organic wools such as resins derived from biomass (biological resources) are known to contain isotopes 14C .
  • the organic solvent living such as animal or plant jwihan all of the organic material is 12 C (from about 98.892 weight 0/0), 13 C (from about 1.108 weight 0/0) and 14 C (from about 1.2 ⁇ a carbon atom ⁇ "contains hamkkae the three kinds of isotope 10 weight 0/0)
  • bieul also kept constant for each isotope, which as equal a high bieul each isotope in the atmosphere, i living organic
  • This isotope ratio is kept constant because the external environment is constantly exchanging carbon atoms while continuing metabolic activity, while 14 C is a radioisotope, and according to the following equation (2), As a result, the content may decrease.
  • the 70 is 14 c represents the initial number of atoms of the isotope, the indicates the number of atoms of 14 c isotope remaining after time, wherein a is the half-life o a related decay constant (or radioactive constant ).
  • Equation 2 the half-life of l C isotope is about 5,730 years.
  • a resin such as an organic material derived from the fossil raw material comprises substantially 14 C isotopes because it includes the time, 14 C isotope hayeoteul estimated according to the equation (2) by more than 0.2% of the initial content (atoms) It can be said that it does not.
  • the denominator may be a weight ratio of the isotope 14 C / 12 C derived from biomass, such as about 1.2 ⁇ 10-12 , the molecule is contained in the resin to be measured 14 It may be a weight ratio of C / 12 C.
  • carbon atoms derived from biomass maintain an isotope weight ratio of about 1 ⁇ 10-12
  • carbon atoms derived from fossil fuels have a substantially zero ratio of these isotope weight ratios.
  • the organic carbon content (% C bio) of the biomass origin among all carbon atoms can be determined by the above Equation 1.
  • the content of each carbon isotope and the content ratio (weight ratio) of each carbon isotope is a standard test method for determining the biobased content of natural materials using ASTM D6866-06 standard (radiocarbon and isotope ratio mass spectrometry analysis).
  • ASTM D6866-06 standard radiocarbon and isotope ratio mass spectrometry analysis.
  • the carbon atoms contained in the resin to be accumulated may be in the form of graphite or carbon dioxide gas and stored by mass spectrometry, or by liquid scintillation spectroscopy.
  • an accelerator for separating 14 c ions from 12 c ions together with the mass spectrometer may be used to separate two isotopes and the content and content ratio of each isotope may be determined by a mass spectrometer.
  • the content and content ratio of each isotope may be obtained by using liquid scintillation spectroscopy that is apparent to those skilled in the art, through which the organic carbon content of Equation 1 may be derived.
  • the polylactic acid resin and the polylactic acid-polyamide alloy resin including the same may be formed in a higher amount of biomass. It is derived from the resin and carbon derived, and can exhibit the characteristic true environmental characteristic and biodegradability suitably.
  • the polylactic acid resin that satisfies such high organic carbon content (% C bio) and the polylactic acid-polyamide alloy resin composition comprising the same may exhibit the true environmental properties described below.
  • Biochemicals, such as polylactic acid resin are biodegradable, with low carbon dioxide emissions and up to 108% less carbon dioxide emissions than current petrochemicals, and up to 50% energy for resin production. Can be saved.
  • bio utilize the biomass raw bio 'When fossil fuels used against ISO 14000 environmental life cycle assessment produces plastic (compliant Life Cycle Analysis, LCA) to lead
  • PET resin produces 3.4 kg of carbon dioxide per kg
  • polylactic acid resin a kind of bioplastic
  • energy consumption is only 56% compared to PET.
  • polylactic acid resin previously known, there was a limitation in application due to low flexibility, etc., and in the case of including other components such as a plasticizer to solve this problem, there was a problem that the advantages as the bioplastics described above were greatly reduced.
  • the polylactic acid resin and the polylactic acid-polyamide alloy resin composition comprising the same can satisfy the advantages of the bioplastics while satisfying the high organic carbon content (% C bio) described above, It can be applied to more various fields by solving problems such as low flexibility. Accordingly, the polylactic acid resin and the polylactic acid-polyamide alloy resin composition containing the same satisfying the high organic carbon content (% C bio) described above have advantages as bioplastics. It can show true environmental characteristics that greatly reduce carbon dioxide generation and energy consumption. Such true environmental properties can be established through, for example, life cycle assessment of the polylactic acid-polyamide alloy resin composition.
  • the polylactic acid-polyamide alloy resin composition the polylactic acid resin has the amount of 14 C isotope of carbon atoms of about 7.2 ⁇ 10 ' ⁇ ⁇ 1.2 to 10 weight ⁇ - 0/0, about 9.6 ⁇ ⁇ "11 to 1.2 ⁇ 10 may be a weight 0/0, preferably about 1.08x 1 coming from 10 to 1.2 ⁇ ⁇ 10% by weight poly (lactic acid) resin is poly resin and carbon black than with such a 14 C isotope is substantially constant mass of cattle The entire resin and carbon can be derived from biomass and can exhibit better biodegradability and metabolic properties.
  • the polylactic acid resin not only the polylactic acid repeating unit of the hard segment is derived from biomass, but the polyolefin-based polyol structural unit of the soft segment may also be derived from biomass.
  • a polyoleic-based pulley structural 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, sugar cane, or tapioca.
  • polylactic acid resins containing a polyolefinic polyol structural unit derived from biomass and polylactic acid-polyamide alloy resins containing the same have a higher organic carbon content (% C bio), for example At least about 90%, black may represent at least about 95% of the organic carbon containing (% C bio).
  • the hard segment derived from the biomass has an organic carbon content (% C bio) of about 90% or more, preferably about 95% to about the biomass-derived organic mass, defined by Equation 1 above. It may be 100%, the soft segment derived from the biomass has an organic carbon content (% C bio) of about 70% or more, preferably about 75% to 95% Can be.
  • the polylactic acid resin included in the polylactic acid-polyamide alloy resin composition has a high organic carbon I content (% C bio) of about 60% or more, and black is about 80% or more.
  • the polylactic acid repeating unit of Formula 1 included in the hard segment may be a polylactic acid homopolymer or a repeating unit forming the polylactic acid homopolymer.
  • Such polylactic acid repeating units can be obtained according to the method for preparing a polylactic acid homopolymer, which is well known to those skilled in the art.
  • L-lactide or D-lactide which is a cyclic two monomer, can be obtained from L-lactic acid or D-lactic acid and ring-opened polymerized, or L-lactic acid or D-oil
  • the acid can be obtained by a direct dehydration polycondensation method.
  • the polylactic acid repeating unit may be prepared to have a non-crystalline by copolymerizing L-lactide and D-lactide in a certain ratio, in order to further improve the heat resistance of the molded article comprising the polylactic acid resin, It is preferable to prepare by the method of single polymerization using either L-lactide or D-lactide.
  • the polylactic acid repeating unit may be obtained by ring-opening polymerization using an L-lactide or D-lactide raw material having an optical purity of 98% or higher, and when the optical purity is less than this, the melting temperature of the polylactic acid resin ( Tm) can be lowered.
  • the polyolefm-based polyol constituent unit is a support for a polymerizing agent (poly (1,2-butadiene) or poly (1,3-butadiene)) obtained by radical polymerization of a monomer such as butadiene ⁇ or a structural unit forming the same.
  • HTPB hydroxyl- terminated polybutadiene
  • it may mean a liquid polybutadiene (hydroxyl- terminated polybutadiene (HTPB)) of molecular weight 1,000 to 5,000 obtained by imparting a hydroxyl group at the terminal and through a hydrogenation reaction.
  • HTPB hydroxyl- terminated polybutadiene
  • prepolymerization of a lactide, diisocyanate or an isocyanate compound of bifunctional group or more The urethane bond may be formed.
  • the polyolefin-based polyol structural units may be linearly or branched to each other to form the polyolefin-based polyol repeating unit through the urethane bond or the ester bond.
  • the reaction molar ratio of the isocyanate group of the hydroxy group h diisocyanate at the terminal of the polyolefin-based polyol structural unit or an isocyanate compound of two or more functional groups may be 1: 0.50 to 1 :(). 99.
  • the terminal hydroxyl time of the polyolefin-based polyol structural unit is about 1: 0.60 to about 1: 0.95, more preferably about 1: 0 to 70: 1 to about 0.90 days of the reaction of the isocyanate group of the isocyanate compound. Can be.
  • the polymer or repeating units which form the polyolefin based polyol constituent units are linearly connected through a urethane bond may be particularly a polyurethane polyol repeating unit, and may have a hydroxyl group at the end thereof.
  • the polyol recombination polyol repeating unit may be used as an initiator in a polymerization process for forming a polylactic acid repeating unit. Can work.
  • the reaction ol ratio of the hydroxyl group: isocyanate group is too high exceeding 0.99, the number of terminal hydroxyl groups of the polyurethane polyol repeating unit is insufficient (for example, 0HV ⁇ 1), and may not function properly as an initiator.
  • the ratio of the hydroxyl group: isocyanate group is excessively low, the number of terminal hydroxyl groups of the polyolefin-based polyol repeating unit is excessively high (e.g., OHV> 35), so that the high molecular weight polylactic acid repeating unit and polylactic acid resin Can be difficult to get.
  • the polyolefin fragment 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 polyolefin-based polyol repeating unit is excessively large or small, the flexibility, moisture resistance, mechanical properties, etc. of the molded article obtained from the polylactic acid resin and the polylactic acid-polyamide alloy resin composition including the same It may not be enough. In addition, since the polylactic acid resin may become difficult to meet appropriate molecular weight characteristics, etc., the processability of the polylactic acid-polyamide alloy resin composition may be reduced, or the flexibility, moisture resistance, or mechanical degradation of the molded article may be reduced. .
  • the isocyanate compound capable of forming a urethane bond by bonding terminal hydroxy group of the polyolefin-based polyol repeating unit it may be a diisocyanate compound or a polyfunctional isocyanate compound having three or more isocyanate groups in a molecule, and is derived from a fossil fuel. can do.
  • diisocyanate compound examples include 1,6-nuxamerylene diisocyanate, 2,4'ruluene diisocyanate, 2,6-ruluene diisocyanate, 1,3-xylene diisocyanate, 1,4-xylene diisocyanate, 1,5-napralene diisocyanate, m-phenylene diisocyanate, P-phenylene diisocyanate, 3,3'- dimeryl -4,4'- diphenylmethane diisocyanate, 4,4'-bisphenylenediiso And cyanate, numermeryl liandiisocyanate, isophorone diisocyanate or hydrogenated diphenyl ethane diisocyanate.
  • the polyfunctional isocyanate compound may include an oligomer of the diisocyanate compound, a polymer of the diisocyanate compound, a cyclic multimer of the diisocyanate compound, and hexamerylene diisocyanate isocyanurate. , That oh
  • various diisocyanate compounds that are well known to those skilled in the art may be used without particular limitation. However, 1,6-nuxamerylene diisocyanate is preferable from an axis surface, such as the provision of flexibility to the polylactic acid resin film.
  • the polylactic acid resin is a block copolymer in which the terminal carboxyl group of the polylactic acid repeating unit included in the hard segment is connected by an ester bond to the terminal hydroxyl group of the polyolenic polyol structural unit included in the soft segment, or the block copolymerization.
  • the terminal carboxyl group of the polylactic acid repeating unit may form a terminal hydroxyiodine ester bond of the polyolefin-based polyol repeating unit.
  • the chemical structure of such block copolymers can be represented by the following general formula (1) or (2):
  • 0 represents a polyolefin-based polyol structural unit
  • U represents a urethane bond
  • E represents an ester. Indicates binding.
  • the polylactic acid resin includes a polyolefin-based polyol structural unit or a repeating unit, such as a polyolefin repeating unit and a polyolefin-based polyol structural unit or a block copolymer in which the repeating unit is combined. While being able to suppress the aspiration, the molded article obtained therefrom can have a wide range of excellent moisture resistance, transparency, mechanical resistance, heat resistance or blocking resistance. Further, the molecular weight distribution, glass transition temperature (Tg), melting temperature (Tm), etc. of the polylactic acid resin may vary depending on whether the polylactic acid structural unit or the repeating unit and the polyolefin-based polyol repeating unit have a block copolymer form. This encroachment can further improve the mechanical properties, flexibility and heat resistance of molded parts.
  • a polyolefin-based polyol structural unit or a repeating unit such as a polyolefin repeating unit and a polyolefin-based polyol structural unit or
  • all of the polylactic acid repeating units included in the polylactic acid resin need not be in the form of a block copolymer combined with the polyolefin-based polyol structural unit or the repeating unit, and at least some of the polylactic acid repeating units may be It may also be in the form of oleic-based polyol structural units or polyunsaturated polylactic acid homopolymers.
  • the polylactic acid resin is a block copolymer in which the terminal carboxyl group of the polylactic acid repeating unit included in the hard segment is connected by a terminal hydroxygiosulf ester bond of the polyoleic polybased structural unit included in the soft segment, or the A mixed wool further comprising a polylactic acid repeating unit, ie, a polylactic acid homopolymer, in a block copolymer in which the block copolymer is linearly or branched connected through a urethane bond, and which is not bound to the polyolefm-based polyol repeating unit. It may be in the form.
  • the polylactic acid resin is 100 parts by weight of the entire premise thereof (when the high weight of the block copolymer described above, optionally a polylactic acid homopolymer is included, the total weight with such a single polymer)
  • the content of the soft segment is excessively high, it may be difficult to provide a high molecular weight polylactic acid resin, which may lower the mechanical properties such as the strength of the molding pain.
  • the glass transition temperature is lowered, the slipperiness (slipping), handling or shape retention characteristics, etc. in the packaging process using the molded article may be inferior.
  • the amount of soft segment is too low, there is a limit to improving the flexibility and moisture resistance of the polylactic acid resin and the polylactic acid molded article, and in particular, the glass transition temperature of the polylactic acid resin may be too high, which may lower the flexibility of the molded article.
  • the polyolefin-based polyol constituent units or repeating units of the soft segment are difficult to properly function as an initiator, resulting in poor polymerization conversion or high molecular weight polylactic acid resins.
  • the pulley lactic acid resin 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 polylactic 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 molecular weight may affect the processability of the polylactic acid-polyamide alloy resin composition described above, the mechanical properties of the molded article, and the like.
  • the melt viscosity is too low may be poor workability to a molded product, and even if the processing into a molded product can be reduced mechanical properties such as strength.
  • the molecular weight is excessively large, the melt viscosity during the welding process is excessively high, which may greatly reduce productivity and processability of the molded product.
  • the polylactic acid resin may have a molecular weight distribution (Mw / Mn) defined as a ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of about 1.60 to 3.0, preferably about 1.80 to 2.15.
  • Mw / Mn molecular weight distribution
  • the polylactic acid resin has such a narrow molecular weight distribution [[ara, extruder, etc.
  • the polylactic acid resin may have a melting temperature (Tm) of about 145 ⁇ 178 ° C, about 160 ⁇ 178 ° C, or about 165 ⁇ 175 0 C.
  • the heat resistance of the molded article containing the polylactic acid resin may be lowered, if too high, high temperature is required during melt processing by extrusion or the like, or the viscosity is too high to process the molding wind, etc. Properties may deteriorate.
  • the polylactic acid resin such as a block copolymer included therein, may have a glass transition temperature (Tg) of about 20 to 55 o C, black to about 25 to 55 0 C, and black to about 30 to 55 o C. .
  • Tg glass transition temperature
  • the flexibility and stiffness of the molded article including the polylactic acid-polyamide alloy resin composition can be properly maintained, and the polylactic acid resin can be preferably used as a molding wind. . If the glass transition temperature of the polylactic acid resin is excessively low, the flexibility of the molded article may be improved, but the granularity (slipping), rat acuteness, and shape retention characteristics during the assembly processing using the molded article may be improved depending on the low point.
  • the blowning resistance and the like may be poor, and therefore, application to a molded article may be inadequate.
  • the glass transition temperature is excessively high, the flexibility of the molding wind is low and the strength is too high, which may result in poor milling of the target product when assembling the molded product.
  • the polylactic acid-polyamide alloy resin composition is less than about 1 weight 0 / o monomer relative to the weight of the polylactic acid resin contained therein (e.g., a lock used to prepare a polylactic acid repeat unit I Tied monomers, etc.) may remain, and more preferably, about 0.01 to 0.5% by weight of monomers may remain.
  • the polylactic acid-polyamide alloy resin composition includes a block copolymer having specific structural properties, a polylactic acid resin, and an oxidation inhibitor including the same, so that most of the lactide monomer used during the manufacturing process is polymerized. Participate in to form a polylactic acid repeating unit, and the depolymerization or decomposition of the polylactic acid resin also does not occur substantially. For this reason, the polylactic acid-polyamide alloy resin wool may contain a residual monomer, such as a residual lactide monomer, in a minimum content.
  • the content of the residual monomer in the composition is about 1% by weight or more, odor problems may occur in the molding process using the polylactic acid-polyamide resin composition, and the final molecular weight of the polylactic acid resin may decrease due to the molding process. It may lead to a decrease in the strength of the molded article, and especially when applied to food packaging products, residual monomers may be sucked out, causing stability problems.
  • Polyamide resin contained in the polylactic acid-polyamide alloy resin composition according to the present invention serves to reinforce the polylactic acid resin.
  • the polyamide resin may be a high stiffness polymer having a polyamide resin as a main component in order to maximize the impact resistance, rigidity, durability, heat resistance, etc. of the polylactic acid resin.
  • the polyamide resin is PA6, PA66, PA11, PA46, PA12, PA1012, PA610, PA69, PA6T, PA6I, PA10T, PA12I, PPA (polyphthalamide), PA MXD 6 (Poly-m-xylene-adipamide) or a mixture thereof Wool or copolymer.
  • polyamide resins include polycaproamide (nylon 6), polytetramerylene-adipamide (nylon 46), polynumericsamylenedidiamide (nylon 66), polyhexamerylliano nodiamide (nylon 69). ), Polynuclear saerylene sebacamide (nylon 610), poly?
  • Proproamide / full linusameryleneadipamide copolymer (nylon 6/66), polyhexamethylenedodecanediamide, polynuclear samethyl Lliandodecaamide (nylon 612), polyundecanoamide (nylon 11), polydodecaamide (nylon 12), polynuclear samrylyl isophthalamide (nylon 61), polynuclear samerylene terephthalamide / poly Hexameryl isophthalamide copolymer (nylon 6T / 6I), polynuclear methylene adipamide / polynuclear sammerylene terephthalamide copolymer (nylon 66 / 6T), polybis (4-aminocyclonucleus) methane dode Carmid (nylon PACM12), pulley Deca Merrill alkylene Te Lev LAL amide (nylon 11T), poly undeca Merrill Allen hex hydro-Te Lev and
  • the polyamide resin may be selected from the group consisting of PA6, PA610, PA1010, PA1012, mixtures and copolymers thereof using a monomer derived from biomass, and most preferably PA1010 may be used. .
  • the polyamide resin preferably has a viscosity number (ISO 307) of 120 to 220, more preferably 120 to 160.
  • ISO 307 a viscosity number
  • the melt viscosity of the polyamide resin is low, so that it can be effectively melt-mixed with the polylactic acid resin, and can be better in terms of balance in moldability, heat resistance and mechanical depression.
  • the polyamide resin together with the polylactic acid resin forms the matrix of the composition of the present invention.
  • the polyamide constant weight of the resin is the polylactic acid-polyamide alloy resin composition may be from 10 to 70 weight 0/0 by weight based on the weight of water, preferably 30 may be about 60% by weight, superior to within this range Compatibility with polylactic acid resin, heat resistance, appearance characteristics and impact strength can be exhibited.
  • the polylactic acid-polyamide alloy resin composition may further include an impact modifier.
  • the impact modifiers include polyamide copolymer impact modifiers, acral impact modifiers, methylmethacrylate-butadiene-styrene (MBS) impact modifiers, styrene-erylene-butadiene-styrene (SEBS) impact modifiers, silicone impact modifiers.
  • MBS methylmethacrylate-butadiene-styrene
  • SEBS styrene-erylene-butadiene-styrene
  • silicone impact modifiers At least one selected from the group consisting of a reinforcing agent and a polyester-based elastomer impact modifier, may be preferably a polyamide copolymer impact modifier, more preferably a polyetherpolyol-polyamide copolymer have.
  • the polyether polyol-polyamide copolymer has excellent compatibility with polyamide and impact resistance expressed and economical, and has excellent elasticity, flexibility and impact resistance.
  • the polyether poly-polyamide copolymer is preferably prepared using a biomass raw material.
  • the polylactic acid-based polyol component is introduced into the polylactic acid resin polymer structure, and thus the polyamide copolymer impact modifier, acral impact modifier, and meryl methacrylate Butadiene-styrene (MBS) impact modifiers, styrene-erylene-Butadiene-styrene (SEBS) impact modifiers, silicone-based impact modifiers and polyester-based elastomer impact modifiers, showing excellent compatibility with any It is not limited to the use of certain impact modifiers.
  • the impact modifier may be included in an amount of 20 parts by weight or less, preferably 0.1 to 20 parts by weight, and more preferably 5 to 10 parts by weight, based on 100 parts by weight of the total of the polylactic acid resin and the polyamide resin.
  • the impact resistance of the polyamide alloy resin composition, the shoes and the heat resistance greatly improved - of the polylactic acid resin, and polyamide resin within this range, compatibility is excellent, and the crude poly (lactic acid) that is. Since the impact modifier lowers the crystallization rate and the crystallization content of the polylactic acid-polyamide alloy resin composition to reduce heat resistance and injection moldability, when the amount of the impact modifier exceeds 20% by weight, And there may be a problem that the appearance of the injection molded article and the like is lowered.
  • the polylactic acid-polyamide alloy resin composition may include an antioxidant.
  • the antioxidant may inhibit yellowing of the polylactic acid resin to improve the appearance of the polylactic acid-polyamide alloy resin composition and the molded article. It is possible to suppress the oxidation or thermal decomposition of the soft segment or the like.
  • the polylactic acid-polyamide alloy resin composition is about 100 to I total amount of monomer (eg, lactic acid or lactide) for the formation of polylactic acid repeating units of the polylactic acid resin.
  • the antioxidant may be included at an I content of 3,000 ppmw, about 100-2,000 ppmw, about 500-1,500 ppmw, or about 1,000-1,500 ppmw.
  • the polylactic acid resin may be yellowed by oxidation of the softening component such as the soft segment, and the appearance of the polylactic acid-polyamide alloy resin composition and the molded article may be poor.
  • the amount of the antioxidant is excessively high, the antioxidant may lower the polymerization rate of lactide and the like, and thus, hard segments including the polylactic acid repeating unit may not be properly generated. Mechanical deterioration may be lowered.
  • the polylactic acid resin and the polylactic acid-polyamide alloy resin composition is obtained by adding the antioxidant in a condensed content during polymerization for the production of polylactic acid resin
  • the polylactic acid-polyamide alloy resin composition may exhibit excellent thermal stability in a molding processing process requiring heating of 180 ° C. or higher with respect to the polylactic acid-polyamide alloy resin composition, thus making it suitable for use in tacted or lactic acid. It is possible to suppress the production of low molecular weight substances such as monomers or cyclic oligomers.
  • the polylactic acid-polyamide alloy resin composition may have an ester repeating unit, and by adding an antioxidant, a heat stabilizer or a polymerization stabilizer, the ester repeating unit is subjected to a high temperature extrusion process or a high temperature polymerization reaction. Oxidation or thermal decomposition at the time of molding can be suppressed.
  • the antioxidant may be one or more selected from the group consisting of hindered phenol (hindered phen) -based antioxidant, amine antioxidant, thio-based antioxidant and phosphite-based antioxidant, other polylactic acid Various antioxidants known to be usable in the polyamide alloy ' resin composition can be used.
  • antioxidants include phosphoric acid, trimethylphosphate and triarylphosphate and ground phosphoric acid thermal stabilizers; 2,6-di-t-butyl—P-cresol, octadecyl-3- (4-hydroxy-3,5-di-t-burylfanyl) propionate, tetrabis [methylene-3- (3, 5-di-t-buryl-4-hydroxyphenal) propionate] methane, 1,3,5-triaryl-2,4,6-tris (3,5-di-t-buryl-4- Hydroxybenzyl) benzene, 3,5-di-t-butyl-4-hydroxybenzylphosphite dieryl ester, 4,4'-burylidene-bis (3-meryl-6-t-burylphenol) , 4,4'-thiobis (3-meryl-6-t-burylphenol) and bis [3,3-bis- (4'-hydroxy- 3'-tert-buryl-phenyl) butanoic acid
  • the polylactic acid-polyamide alloy resin composition may contain various known hydrolyzable agents, nucleating agents, organic or inorganic fillers, plasticizers, chain extenders, Various additives, such as an ultraviolet stabilizer, a coloring agent, a matting agent, a mouse, a flame retardant, a weathering agent, an antistatic agent, a mold release agent, an antioxidant, an ion exchanger, a coloring pigment, inorganic or organic particle
  • the hydrolysis agent is a reactive compound capable of reacting with a hydroxyl group or a carboxyl group which is a terminal component of the polylactic acid, thereby improving hydrolysis resistance and durability of the polylactic acid-polyamide resin composition wool. That is, the hydrolysis agent is applied to a resin such as polyester, polyamide, polyurethane, etc., and performs endcapping reaction at the end of the polymer chain to prevent hydrolysis of the resin composition by water or acid. do.
  • the hydrolysis agent may be a carbodiimide-based compound, such as modified phenylcarbodiimide, poly (tolalcarbodiimide), poly (4,4'-diphenylmethanecarbodiimide), poly (3, 3'-dimeryl-4,4'-biphenylene ⁇ bodiimide), poly (P-phenyllian carbodiimide), poly (m-panylene carbodiimide), poly (3,3'-dimeryl- 4,4'-diphenylmethanecarbodiimide).
  • the hydrolysis agent may be added within 5% by weight based on the total weight of the polylactic acid resin and the polyamide resin.
  • the nucleating agent is a polylactic acid-polyamide Earl total weight of the Roy resin composition may contain less than 10 parts by weight 0/0 with respect to (including the nucleating agent), preferably can contain up to 5% by weight, if within the range of heat resistance and injection There is an effect that the moldability is further improved.
  • the nucleating agent sorbitol-based metal salts, phosphate-based metal salts, quinacridone, calcium carboxylate, amide-based organic compounds and the like can be used, and preferably phosphate-based metal salts can be used.
  • plasticizer examples include phthalic ester plasticizers such as phthalic acid diaryl, dioxyl phthalate and dicyclonuclear phthalate; Adiponic Acid Di-1-Buryl, Adipic Acid Di-n-Oct, Sebacic Acid Di-n-Buryl, Ar Aliphatic dibasic acid ester-based plasticizers such as zeline acid di-2-ethylnuclear chamber; Phosphate ester plasticizers, such as diphenyl 2- aryl hexyl phosphate and diphenyl oxyl phosphate; Hydroxy polyhydric carboxylic acid ester plasticizers such as aceryl citric acid triburyl, aceryl citric acid tri-2-eryyl nucleus, and citric acid triburyl; Fatty acid ester plasticizers such as aceryl ricinolic acid meryl and stearic acid wheat; Polyhydric alcohol ester plasticizers such as glycerin triacetate; Epoxy plasticizers, such as
  • examples of the colored pigment include inorganic pigments such as carbon block, titanium oxide, zinc oxide and iron oxide; Organic pigments such as cyanine-based, phosphorus-based, quinone-based, lerione-based, isoindolinone-based and geo-indigo-based;
  • the inorganic or organic particles are the polylactic acid - may contain less than 30 wt% based on the total weight of the polyamide alloy resin composition, it may be included within preferably 10 wt. 0/0.
  • the inorganic or organic particles include silica, colloidal silica, alumina, alumina sol, talc, titanium dioxide, mica, calcium carbonate, polystyrene, polymer methacrylate, silicone Etc. can be mentioned.
  • the silica, titanium dioxide or lalc is not limited to the surface affinity, but when using surface-fed titanium dioxide or talc, not only the excellent total balance including stiffness and impact strength, but also lowering the specific gravity, It is effective in improving heat resistance and injection moldability.
  • the surface preparation can be carried out by a chemical or physical method using a treatment agent such as silane coupling agent, higher fatty acid, metal salt of fatty acid, unsaturated fatty acid, organic titanate, resin acid, polyylene glycol, and the like.
  • the inorganic particles may have an average particle size of 1 to 30 um, preferably 1 to 15 urn, and has an effect of improving heat resistance and rigidity within the above range.
  • the polylactic acid-polyamide alloy resin composition may have a color-b value of less than 15 in a chip state, and preferably 10 or less. Since the polylactic acid-polyamide alloy resin composition includes an antioxidant, yellowing of the polylactic acid resin may be suppressed, and thus a color-b value of less than 15 may be exhibited. If the color-b value of the polylactic acid-polyamide alloy resin wool is 15 or more, the appearance of the molded product may be poor when used for molding, and the product branches may fall.
  • the manufacturing method of the polylactic acid-polyamide copolymer alloy resin composition of this invention is demonstrated concretely.
  • a hydroxyl group is imparted to the terminal of a polymer (poly (1,2-butadiene) or poly (1,3-butadiene)) obtained by radical polymerization of a butadiene monomer, and then subjected to a hydrogenation reaction to have a molecular weight in the range of 1,000-3,000.
  • a liquid polybutadiene (HTPB) to obtain a (co) polymer having a polyolefin based polyol structural unit. This can be carried out according to a conventional method for preparing a polyolefin-based polyol (co) polymer.
  • a (co) polymer, polyfunctional isocyanate compound wool and a urethane reaction catalyst having the polyolefin-based polyol structural unit are charged to the reactor, and the urethane reaction is performed by heating and stirring. Under such a reaction, two or more isocyanate groups of the isocyanate compound and terminal hydroxyl groups of the (co) polymer are bonded to form a urethane bond.
  • a (co) polymer having a polyurethane polyol repeating unit in which polyolefin-based polyol structural units are linearly or branched connected through the urethane bond can be formed. This is included as a soft segment of the polylactic acid resin described above.
  • the polyurethane polyol (co) polymerizer is a polyolefin-based polyol structural unit (0) is 0-U-0-U-0 or 0-U (-0) -0 through the urethane bond (U) It may be combined in a linear or branched form in the form of -U-0 to form a polyolefin-based polyol structural unit at both ends.
  • a (co) polymer a lactic acid (D- or L-lactic acid) or lactide (D- or L-lactide) compound and a condensation or ring-opening reaction catalyst having the polyolefin fragment polyol unit It is added to the mixture, heated and stirred to carry out the polyester reaction or the ring-opening polymerization reaction.
  • the lactic acid (D- or L-lactic acid) or lactide (D- or L-lactide) and the terminal hydroxyl group of the (co) polymer bond to form an ester bond.
  • a (co) polymerizer may be formed in which the polyolefin-based polyol structural units are connected in a linear or branched polylactic acid repeating unit via the ester bond.
  • the (co) polymerization agent is a polyolefin-based polyol structural units ( ⁇ ) is linearly bonded in the form of polylactic acid repeat unit (L) and LE-0-EL via the ester bond (E) to the polylactic acid at both ends It may be formed in the form having a repeating unit. Thereafter, two or more isocyanate groups of the isocyanate compound bind the terminal hydroxyl group of the (co) polymer to form a urethane bond (U) to form LE-EL ELULE-0-EL.
  • Polylactic acid resin can be prepared by linear or branched bonding.
  • the polyolefin-based polyol repeating units obtained from the butadiene may be derived from biomass such as resources to cool, and thus polyolefin-based polyol
  • the (co) polymer may have a value that is significantly higher, with an organic carbon content (% Cbio) of biomass origin of about 70% or more.
  • the urethane reaction may be carried out in the presence of a conventional tin-based catalyst, for example, stannous octoate, dibutyltin diiaurate, dioctyltin diiaurate, and the like.
  • a conventional tin-based catalyst for example, stannous octoate, dibutyltin diiaurate, dioctyltin diiaurate, and the like.
  • the urethane reaction may be carried out under the reaction conditions for preparing a conventional polyurethane resin. For example, after adding the isocyanate compound and the polyolepun-based polyol (co) polymer in a nitrogen atmosphere, the urethane reaction catalyst is added and reacted for 1 to 5 hours at a reaction temperature of 70 to 80 ° C.
  • the (co) polymer which has all repeating units can be manufactured.
  • the above-described block copolymer (or polylactic acid resin including the same) may be prepared. That is, when such a polymerization reaction is performed, a polylactic acid resin having a polylactic acid repeating unit included as a hard segment is produced while the yellowing caused by oxidation of the soft segment is suppressed by the antioxidant, and at least a part of the polylactic acid is produced.
  • the polyurethane polyol repeating unit may be bonded to the end of the repeating unit to form a block copolymer.
  • Known branched block copolymers may be formed that react with water.
  • the lactide ring-opening polymerization reaction may be performed in the presence of a metal catalyst including an alkaline earth metal, a rare earth metal, a transition metal, an aluminate, a germanium, tin, or an antiion.
  • a metal catalyst including an alkaline earth metal, a rare earth metal, a transition metal, an aluminate, a germanium, tin, or an antiion.
  • metal catalysts may be in the form of carbonates, alkoxides, halides, oxides, carbonates, and the like of these metals.
  • tin octylate, titanium tetraisopropoxide, aluminium triisopropoxide, or the like can be used as the metal catalyst.
  • the polylactic acid repeating unit forming step such as the lactide ring-opening polymerization reaction may be continuously performed in the same reactor in which the urethane reaction proceeds. That is, a polyolefin-based polyol polymer and an isocyanate compound are urethane-reacted to form a polymer having a polyolefin-based polyol repeating unit, and then a monomer and a catalyst such as lactide in the reactor. And the like can be added continuously to form a polylactic acid repeating unit.
  • the polylactic acid repeating unit and the polylactic acid resin containing the same can be continuously produced with high number and productivity.
  • the chain extension polymerization is carried out by adding isocyanate compounding continuously in the same reactor to repeat the polylactic acid repeating unit and the polylactic acid resin including the same. It can be produced continuously with high numbers and high productivity.
  • the polylactic acid resin thus prepared may be mixed with a polyamide resin and other materials to prepare a polylactic acid-polyamide alloy resin composition.
  • the polylactic acid-polyamide alloy resin composition described above includes a block copolymer (pully lactic acid resin) in which specific hard and soft segments are bonded, thereby exhibiting the biodegradability of the polylactic acid resin, while providing improved flexibility. Can be represented. In addition, the suction of the soft segment to give flexibility can be minimized, and the addition of the soft segment also greatly reduces the moisture resistance, mechanical resistance, heat resistance, transparency, or haze characteristics of the molded article. Can be.
  • the polylactic acid resin is manufactured to have a predetermined glass transition temperature and optionally a predetermined melting temperature
  • the molded article obtained therefrom may exhibit constricted flexibility and stiffness as a packaging material, as well as melting.
  • the workability is also excellent, and the blocking resistance and heat resistance are further improved. Therefore, such a polylactic acid resin and the polylactic acid-polyamide alloy resin composition including the same can be very preferably applied to packaging materials such as molded articles.
  • the pulley lactic acid resin is included with an antioxidant, and yellowing can be suppressed during the manufacturing or use process, and polylactic acid polyamide alloy resin composition containing these components exhibits an excellent appearance and products, It is possible to provide molded articles exhibiting various physical properties such as flexibility and excellent mechanical properties.
  • the polylactic acid- pullyamide alloy resin composition of the present invention includes a polyolefin-based polyol repeating unit as a soft segment, the flexibility of a molded article manufactured using the polylactic acid-polyamide alloy resin composition is greatly improved. Can be.
  • the moisture resistance can be greatly improved by lowering the moisture content in the whole resin due to the non-polar soft segmented polyol reffin-based polyol repeating unit.
  • -HTPB 1.0 A hydroxyl group is imparted to the terminal of a polymerizing agent (poly (1,2-butadiene) or poly (1,3-butadiene)) obtained by radical polymerization of butadiene monomer, and is obtained through hydrogenation reaction.
  • a polymerizing agent poly (1,2-butadiene) or poly (1,3-butadiene
  • HTPB Hydroxyl-terminated polybutadiene
  • HTPB 2.0 A hydroxyl group is added to the terminal of a polymerizing agent (poly (1,2-butadiene) or poly (1,3-butadiene)) obtained by radical polymerization of a butadiene monomer, and is obtained through hydrogenation reaction.
  • a polymerizing agent poly (1,2-butadiene) or poly (1,3-butadiene
  • HTPB Liquid polybutadiene
  • -HTPB 3.0 A hydroxyl group is imparted to the terminal of a polymerizing agent (poly (1,2-butadiene) or poly (1,3-butadiene)) obtained by radical polymerization of a butadiene monomer, and is obtained through a hydrogenation reaction.
  • a polymerizing agent poly (1,2-butadiene) or poly (1,3-butadiene
  • Liquid polybutadiene (HTPB) with a molecular weight of 3,000
  • -HTPB 5.0 A hydroxyl group is added to the terminal of a polymerizing agent (poly (1,2-butadiene) or poly (1,3-butadiene)) obtained by radical polymerization of a butadiene monomer, and is obtained through a hydrogenation reaction.
  • a polymerizing agent poly (1,2-butadiene) or poly (1,3-butadiene
  • HTPB Liquid Flipbutadiene
  • PTMG 3.0 pulley tetramerylene glycol; Number average molecular weight 3,000
  • PBSA 11.0 aliphatic polyester polyols made of 1,4-butanediol and a condensation agent of succinic acid and adipic acid; Number average molecular weight ⁇ , ⁇
  • TDI 2,4- or 2,6-tolylene diisocyanate (toluene diisocyanate: TDI)
  • D-L75 Vialsa desmodur L75 (trimerololpropane + 3 toluene diisocy) Anate)
  • L-lactide or D-lactide Purac, with an optical purity of at least 99.5%
  • TNPP tris (nonylphenyl) phosphite
  • PA1010 Polyamide resin made by polycondensation reaction of 1,10-decamerylene diamine derived from biomass with 1,10-degandioic acid (sebacic acid), viscosity number 120 cmVg, bio content 100 %
  • PA66 polyamide resin made by polycondensation of petroleum based 1,6-nuxamerylene diamine and 1,6-nucleodiode acid (adipic acid), viscosity degree 200 cm 3 / g, bio content 0%
  • -Pebax 63R53 SP01 poly (1,3-propanediol) -polyamide block copolymer, Akema, hardness 56 HD (Shore D, 15s), bio content 80% -AX8840: ethylene-maleic anhydride graft-glycidyl methacrylate copolymer, Akemain g graft rate 8.0%
  • TF-1 ⁇ , ⁇ , ⁇ '-tricyclonuclear chamber-1,3,5-benzenetricarboxamide, NJC Corporation
  • NA-11 2,2'-merylene bis (4,6-di-tert-burylphenol) sodium phosphate, Asahi Denka ( ⁇
  • BioAdimide 100 carbodiimide-based polymer, Rhein Chemie
  • ADR 4368 styrene-acryl polymer, BASF
  • reaction wools having the components and contents as shown in Table 1 below were packed together with the ammonia. 130 ppmw of dibutyltin dilaurate was used as the catalyst. Urethane reaction was carried out for 2 hours at a reactor temperature of 70 ° C. under nitrogen stream, and 4 kg of L- (or D-) lactide was added thereto to carry out No. 5 I flushing.
  • the reaction was carried out at 185 0 C under a 1 kg nitrogen pressurization for 2 hours, 200 ppmw of phosphoric acid was added to the catalyst inlet, and then mixed for 15 minutes to inactivate the residual catalyst. The reaction was vacuumed until it reached 0.5 torr. Unreacted L-lactide (about S parts by weight of the initial dose) was removed via. Thereafter, HDI and 120 ppmw of the catalyst dibutylene dilaurate as shown in Table 1 were diluted with 500 ml of toluene and added into the reaction vessel through the ammonia inlet. The reaction was carried out at 190 ° C. for 1 hour in a nitrogen atmosphere, and the molecular weight characteristics, Tg, Tm, and% C by 2 of the obtained resin were measured and shown in Table 1 below.
  • the preparation was carried out in the same manner as in Production Example 10, except that 6 g of 1-dodeganol was added instead of the polyol.
  • the molecular weight characteristics, Tg, Tm and% C by £ of the obtained resin were measured and shown in Table 1.
  • the polylactic acid resin prepared in Preparation Examples 1 to 12 was vacuum at 1 torr for 6 hours at 80 ° C. After drying under reduced pressure, the polyamide resin and other materials are mixed using a super mixer as described in Tables 2 or 3, which are subjected to a 19 mm diameter twin screw extruder (single screw extruder, mill, kneader or banbury). Melt kneading was extruded onto strands at an extrusion temperature of 230 to 260 ° C. in a blending machine such as a mixer. Strands chopped through a water bath were prepared in pellet form using a pelletizer. This was dried at 80 ° C. for at least 4 hours with a dehumidifying dryer or a hot air dryer, followed by injection molding to prepare a specimen. The evaluation result of the obtained molded article is shown in Table 2 or 3.
  • NCO / OH "Isocyanate compound (e.g., numermerylene diisocyanate) to form I-isocyanate group / polyether-based polyol repeating unit (or (co) polymer) for forming polyolefinic polyol repeating unit Rebellion olby of the "hydroxy group”.
  • Isocyanate compound e.g., numermerylene diisocyanate
  • polyether-based polyol repeating unit or (co) polymer
  • OHV OHmg / g: Polyolefin-based polyol repeating unit (or (co) polymer) is dissolved in dichloromethane and then acetylated, and acetic acid produced by hydrolysis is titrated with 0.1N OH methanol solution. It was. This corresponds to the number of hydroxy groups present at the I terminus of the polyolefin fragment polyol repeating unit (or (co) polymer).
  • the molecular weight distribution value (MWD) was calculated from the Mw and Mn thus calculated.
  • Tg Glass Transition Temperature, ° C: Measured by using a Shisa scanning calorimeter (TA Instruments) after the sample was melted and rapidly heated to 10 ° C / min. The base line near the endothermic curve and the mid value of each tangent line were Tg.
  • Tm melting temperature, ° C: Using a differential scanning calorimeter (TA Instruments), the sample was melt quenched and then heated to 10 ° C./min to condense. The maximum value temperature of the melting endothermic peak of the crystal was Tm.
  • Residual Monomer (Lactide) Content 0.1 g of the resin was dissolved in 4 ml of chloroform, and 10 ml of nucleic acid was filtered and quantified by GC analysis.
  • Chip color-b After calculating the value using a color difference meter (CR-410, onica Minolta Sensing Co., Ltd.) for the resin chip, a total of five average tests were displayed.
  • a color difference meter CR-410, onica Minolta Sensing Co., Ltd.
  • Extrusion state After extruded polylactic acid-polyamide resin into strands at an extrusion temperature of 230 to 260 ° C in a 30 mm diameter twin screw extruder equipped with a hole die. Solidified in a 20 ° C angle angle bath. At this time, the melt viscosity of the discharge on the strand and the uniformity of the melt were visually evaluated and the state of the melt viscosity (extrusion state) was evaluated according to the following criteria.
  • Ml melting index: According to ASTM D1238, the average value of the three tests in total at 2.16 kgf load at a temperature of 220 ° C. was expressed as the result sheet.
  • ⁇ Good phase separation between two resins and undispersed resin particle size 0.2 ⁇ m or less
  • ⁇ Good phase separation between two resins and undispersed resin particle size 1.0 ⁇ or less
  • phase separation between two resins is poor, and the particle size of undispersed resin is 1.0 ⁇ or more.
  • Elongation (%) The elongation until fracture of the specimen was calculated under the same conditions as the initial tensile strength of (14).
  • High temperature mold 110 o C high temperature mold was used for injection, and within 30 seconds each time ⁇ ) Low temperature mold: normal temperature mold was used for injection, and within 30 seconds cooling time
  • Anti-bleed out The degree to which the low molecular weight plasticizer component was aspirated by the shrinkage by shrinking the surface of the molded product to the mold H surface was evaluated according to the following criteria using an A4 size film sample.
  • Moisture resistance retention (%): The initial tensile strength change was determined after 30 days of 150 mm in length and 10 mm in width at 40 ° C. and 90% RH in I atmosphere.
  • Example 6 is a polylactic acid-polylactic acid-a polylactic acid resin (resin F) corresponding to the polylactic acid resin contained in the polyamide alloy resin composition of the present invention and a polylactic acid-containing a general polylactic acid resin (resin K)- It was prepared using the polyamide alloy resin composition.
  • resin F polylactic acid-polylactic acid-a polylactic acid resin
  • resin K polylactic acid-containing a general polylactic acid resin
  • All of the injection molded articles of Examples 1 to 8 have an initial tensile strength of 300 kgf / cm 2 or more, an impact strength of 25 kg cm / cm or more, and excellent mechanical properties, and high temperature mold HDT of 85 0 C or more. It showed excellent heat resistance. After 30 days in an atmosphere of 40 ° C. and a humidity of 90% RH, the moisture-resistant tensile strength retention was excellent at 80% or more, and no bleeding phenomenon occurred. In addition, the organic carbon content of the resin is more than 60% can be called a true environment material. In contrast, the injection molded article of Comparative Example 1 made of polylactic acid-polyamide alloy resin containing polylactic acid resin A included in the polylactic acid-polyamide alloy resin composition of the present invention has good physical properties.
  • the organic carbon content is less than 25%, which does not meet the global environmental plastic standards.
  • the extruded ronal resins of Comparative Examples 2 and 3 prepared from a polylactic acid-polyamide alloy resin composition containing a general polylactic acid resin K have poor compatibility with the polylactic acid resin polyamide resin and are both resins. The difference in melt viscosity between the two was so large that it was difficult to be used as an injection molded product due to poor extrusion conditions such as die swelling during extrusion kneading.
  • Comparative Examples 6 and 7 repeat the polyolefin-based polyol which is a flexible resin component in the polylactic acid resin.
  • Aliphatic polyester polyols made of no plasticizer components, made of poly (1,3-propanediol) having a number average molecular weight of 2,400 and 1,4-butanediol having a number average molecular weight of 11,000 and condensing agents of succinic acid and adipic acid, respectively, Injection molding is carried out by simply compounding the polylactic acid resin K.
  • the injection molded article of Comparative Example 8 was prepared from a polylactic acid-polyamide alloy resin including a polylactic acid resin having a polyester polyol repeating step and a wide molecular weight distribution.
  • the injection molded article of Comparative Example 8 exhibited relatively good resistance to adsorption as the softening component polyurethane was randomly introduced into a small segment size, the polylactic acid repeat unit was introduced into a relatively small segment size. It exhibited poor heat resistance due to and the like, and had poor mechanical strength due to compatibility problems.
  • FIG. 4 clearly shows a distinction between polylactic acid resin and polyamide resin, and shows poor air compatibility (pore) due to die swelling during melt kneading between two resins. have. Since such a resin cannot obtain a uniform pressure line, strand and pellet production becomes difficult to control.
  • the polylactic acid-polyamide resin composition has the impact resistance, which is a weak point of the polylactic acid resin, due to the increased dispersibility in the polyamide resin or the polyamide resin in the polylactic acid resin.
  • the crystallization rate and heat resistance of the resin composition can be improved to achieve the overall physical balance of the resin composition.

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  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention porte sur une composition de résine d'alliage de poly(acide lactique)-polyamide contenant 30 à 90 parties en poids d'une résine de poly(acide lactique) et 10 à 70 parties en poids d'une résine de polyamide, la résine de poly(acide lactique) comprenant un segment rigide comprenant un motif répété poly(acide lactique) et un segment souple comprenant un motif répété polyol à base de polyoléfine dans lequel les motifs constitutifs polyols à base de polyoléfine sont reliés sous une forme linéaire ou ramifiée par l'intermédiaire d'une liaison uréthane ou d'une liaison ester, et le pourcentage de carbone organique issu de biomasse de la résine de poly(acide lactique) est supérieur ou égal à 60 %. La résine d'alliage de poly(acide lactique)-polyamide selon la présente invention présente une résistance au choc supérieure ainsi que d'excellentes propriétés notamment la résistance à la chaleur, la résistance à l'humidité, les propriétés mécaniques et l'aptitude au moulage par injection, et donc peut être utile comme matériau pour un article moulé, et a des caractéristiques respectueuses de l'environnement et donc peut grandement contribuer à la prévention de la pollution environnementale.
PCT/KR2014/010076 2013-10-25 2014-10-24 Composition de résine d'alliage de poly(acide lactique)-polyamide WO2015060689A1 (fr)

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KR10-2013-0128001 2013-10-25

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KR102239881B1 (ko) * 2019-12-27 2021-04-14 주식회사 삼양사 내마찰성능이 향상된 고강성 폴리아미드 수지 조성물 및 이를 포함하는 성형품
CN113402864B (zh) * 2020-03-16 2022-07-15 中国科学院化学研究所 一种增韧型聚乳酸塑料及其制备方法
CN113354931A (zh) * 2021-06-11 2021-09-07 晋江凯基高分子材料有限公司 一种pla改性材料的制备方法

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TW201527420A (zh) 2015-07-16
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KR102103524B1 (ko) 2020-04-22

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