WO2018008969A1 - Composition d'acide polylactique pour filament d'imprimante tridimensionnelle, ayant une vitesse d'impression améliorée - Google Patents

Composition d'acide polylactique pour filament d'imprimante tridimensionnelle, ayant une vitesse d'impression améliorée Download PDF

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WO2018008969A1
WO2018008969A1 PCT/KR2017/007162 KR2017007162W WO2018008969A1 WO 2018008969 A1 WO2018008969 A1 WO 2018008969A1 KR 2017007162 W KR2017007162 W KR 2017007162W WO 2018008969 A1 WO2018008969 A1 WO 2018008969A1
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polylactic acid
weight
resin
dimensional printer
filament
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PCT/KR2017/007162
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English (en)
Korean (ko)
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이열
이수현
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롯데케미칼 주식회사
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Priority claimed from KR1020160084794A external-priority patent/KR101812884B1/ko
Application filed by 롯데케미칼 주식회사 filed Critical 롯데케미칼 주식회사
Priority to CN201780048336.7A priority Critical patent/CN109563332A/zh
Publication of WO2018008969A1 publication Critical patent/WO2018008969A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B11/00—Making preforms
    • B29B11/06—Making preforms by moulding the material
    • B29B11/10—Extrusion moulding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C67/00—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • C08K5/134—Phenols containing ester groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • 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

Definitions

  • the present invention relates to a polylactic acid composition for three-dimensional printer filament, and more particularly to a polylactic acid composition that contributes to an increase in the three-dimensional printer output speed increase by increasing the crystallization rate of the resin.
  • 3D (3-Dimensional) printer is a device that manufactures three-dimensional shape by stacking layers with fine thickness by sequentially spraying ink of special material. Three-dimensional printing is spreading in various fields. In addition to the automotive field, which is made up of many parts, it is used by many manufacturers to create various models of medical human models, household products such as toothbrushes and razors.
  • the most widely used material for 3D printing is 'photopolymer', a photocurable polymer material that hardens when subjected to light. This accounts for 56% of the total market.
  • the next most popular material is a solid thermoplastic that is free to melt and harden, accounting for 40% of the market, and metal powder is expected to grow in the future.
  • the form of the dual thermoplastic material may have a filament, particle or powder form. The three-dimensional printing of the filament type is faster than the other types in terms of speed, so the productivity is high and the diffusion speed is fast.
  • polylactic acid has a slow crystallization characteristic, and thus has a limitation of slow 3D printing.
  • commercialized polylactic acid filament has a great inconvenience of printing about 10 hours at the time of printing based on the weight of about 35g, size 70 ⁇ 61 ⁇ 64mm.
  • Korean Patent Laid-Open No. 2012-0108798 is an L-type and D-type polylactic acid stereocomposite in which the crystallization rate is improved by cooling the surface of the mold cavity to 100-110 ° C and cooling the stereocomposite crystal.
  • the melting temperature is 190 ⁇ 195 °C, but its use is limited to automotive materials, and it is not mentioned in the application of the 3D printer filament, and the cost burden is caused by the use of D-type polylactic acid. .
  • Korean Patent Publication No. 2012-0129500 discloses a polylactic acid composition having improved mechanical properties and crystallization rate by applying a naturalized surface-treated natural stone powder and carbon nanotubes to polylactic acid, and as a nucleating agent for improving the crystallization rate.
  • a naturalized surface-treated natural stone powder and carbon nanotubes to polylactic acid, and as a nucleating agent for improving the crystallization rate.
  • the use of carbon nanotubes is not suitable as a material for three-dimensional printers that require various colors.
  • Korean Laid-Open Patent Publication No. 2012-0022420 relates to a method for producing a heat-resistant polylactic acid fiber mixed with an L-type polylactic acid, D-type polylactic acid, and polyester, and to a fiber of a heat-resistant polylactic acid stereo complex through high temperature heat treatment.
  • an application method is disclosed, its use is limited to stretched fibers and does not mention the application of a filament for a three-dimensional printer, and cost burden is a problem by using a D-type polylactic acid.
  • the present invention has been made to solve the above problems, a nucleating agent of a specific composition and (i) amorphous resin, (ii) a polyolefin resin having at least one hydrophilic functional group and (iii) additives for the purpose of preventing oxidation It is to provide a polylactic acid composition for three-dimensional printer filaments that contribute to the increase in the three-dimensional printer output speed increase by increasing the crystallization rate of the resin through at least one addition selected from the group consisting of.
  • 1st aspect of this invention is a polylactic acid composition for three-dimensional printer filaments, (A) 95-99.9 weight% of polylactic acid resin; (B) 0.1 to 5% by weight of the nucleating agent; And (i) 0.1 to 10.0 parts by weight of amorphous resin based on 100 parts by weight of the polylactic acid resin (A) and the nucleating agent (B). (ii) 0.1 to 10 parts by weight of a polyolefin resin having at least one hydrophilic functional group; and (iii) 0.01 to 2.0 parts by weight of an additive for the purpose of anti-oxidation. It provides a lactic acid composition.
  • the (A) polylactic acid resin in the group consisting of poly-L-lactic acid (PLLA), poly-D-lactic acid (PDLA), stereo complex PLA (stereo complex PLA) and stereo block PLA (stereo block PLA) It provides a polylactic acid composition for three-dimensional printer filament, characterized in that at least one selected.
  • PLLA poly-L-lactic acid
  • PDLA poly-D-lactic acid
  • stereo complex PLA stereo complex PLA
  • stereo block PLA stereo block PLA
  • the (B) nucleating agent may be a talc nucleating agent, a sodium phosphate talc nucleating agent, a phenylorganic zinc phosphate nucleating agent, a phenyl organic phosphate zinc salt type-zinc oxide type nucleating agent and a sodium phosphate salt- aromatic organic phosphate type- It provides a polylactic acid composition for a three-dimensional printer filament, characterized in that at least one selected from the group consisting of calcium salt-based nucleating agent.
  • the nucleating agent (B) is three-dimensional, characterized in that methylenebis (4,6-di-tert-butylphenol) sodium phosphate (methylenebis (4,6-di-tert-butylphenol) phosphate sodium salt) It provides a polylactic acid composition for a printer filament.
  • the (ii) amorphous resin is a polycarbonate, acrylonitrile butadiene styrene copolymer, polystyrene, styrene acrylonitrile copolymer, acrylonitrile styrene acrylate (acrylonitrile styrene acrylate) copolymer, polymethyl methacrylate (polymethyl methacrylate), polysulfone (polysulfone) and polyethersulfone (polyethersulfone) polylactic acid for three-dimensional printer filament characterized in that at least one selected from the group consisting of To provide a composition.
  • the polyolefin resin having at least one hydrophilic functional group provides a polylactic acid composition for three-dimensional printer filament, characterized in that the content of the hydrophilic functional group is 0.1 to 10% by weight.
  • hydrophilic functional group is characterized in that selected from the group consisting of acrylic (maleic anhydride), amine (amine), carbonyl (carbonyl), hydroxyl (hydroxyl) and carboxyl (carboxyl)
  • acrylic maleic anhydride
  • amine amine
  • carbonyl carbonyl
  • hydroxyl hydroxyl
  • carboxyl carboxyl
  • the polyolefin resin provides a polylactic acid composition for a three-dimensional printer filament, characterized in that the ethylene vinyl acetate (EVA) resin having maleic anhydride as the hydrophilic functional group.
  • EVA ethylene vinyl acetate
  • the additive for the purpose of antioxidant is a polylactic acid for three-dimensional printer filament, characterized in that at least one selected from the group consisting of phenolic antioxidant, phosphorus antioxidant and phenol-phosphorus complex antioxidant To provide a composition.
  • the additive for the purpose of (C) oxidation prevention is tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane (Tetrakis [methylene-3] It provides-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane) polylactic acid composition for three-dimensional printer filament.
  • the ethylene vinyl acetate (EVA) resin provides a polylactic acid composition for three-dimensional printer filament, characterized in that the melt index (ASTM D 1238, 190 °C, 2.16kg) is 10 ⁇ 15g / 10min.
  • commercialization comprising a block copolymer or a graft copolymer for forming a microphase separation structure between the (A) polylactic acid resin and the (ii) amorphous resin or (iii) a resin having at least one hydrophilic functional group.
  • the agent provides a polylactic acid composition for a three-dimensional printer filament, comprising 0.5 to 10 parts by weight based on 100 parts by weight of the total polylactic acid composition.
  • the block copolymer may be a styrene-ethylene / butylene / styrene (SEBS) block copolymer, a styrene-ethylene / propylene-styrene (SEPS) block copolymer, a methacrylic block copolymer, a polycaprolactone polyester copolymer, It provides a polylactic acid composition for three-dimensional printer filament, characterized in that at least one member selected from the group consisting of polycaprolactone polyester / poly (tetramethylene glycol) block polyol copolymer and methacrylate polystyrene copolymer.
  • SEBS styrene-ethylene / butylene / styrene
  • SEPS styrene-ethylene / propylene-styrene
  • methacrylic block copolymer a polycaprolactone polyester copolymer
  • the graft copolymer is one or more selected from the group consisting of polypropylene-maleic anhydride graft copolymer, polyethylene-maleic anhydride graft copolymer and polyethylene-glycidyl methacrylate graft copolymer It provides a polylactic acid composition for a three-dimensional printer filament characterized in that.
  • the polylactic acid composition provides a polylactic acid composition for a three-dimensional printer filament, characterized in that less than 200 seconds when the crystallization time evaluation using a differential scanning calorimetry (110 °C).
  • the present invention provides a polylactic acid composition for a three-dimensional printer filament characterized in that the surface transition phenomenon of the resin does not occur when the output under the following conditions using the filament made of the polylactic acid composition.
  • the second aspect of the present invention provides a three-dimensional printer filament comprising the polylactic acid composition of any one of claims 1 to 13.
  • the filament is a screw diameter 20 ⁇ 40mm, using a single screw or twin screw extruder having a screw length of 100 ⁇ 110mm, it is manufactured by cooling using a melt extrusion and a cooling water bath at a temperature of 170 ⁇ 200 °C 3 Provides dimensional printer filaments.
  • the filament is molded into a diameter of 1.5 ⁇ 2mm provides a three-dimensional printer filament characterized in that the winding.
  • the present invention it is possible to provide a three-dimensional printer filament having a good mechanical properties by improving the crystallization rate by mixing a suitable amount of a specific nucleating agent or amorphous resin in the polylactic acid resin.
  • 1 is a view showing the formation process of L-type PLA and D-type PLA structure and stereo complex PLA
  • Figure 2 is a view showing the crystallization time measurement results at 110 °C the resin composition prepared according to Examples 1 to 7 and Comparative Example 1,
  • FIG. 3 is a photograph of the filament of Comparative Example 2 set at a condition temperature of 200 ° C., an initial speed of 15 mm / s, an output speed of 40 mm / s, and a time for outputting one layer of 30 seconds;
  • FIG. 4 is a photograph of the filament of Comparative Example 2 set to a condition temperature of 200 ° C., an initial speed of 15 mm / s, an output speed of 110 mm / s, and a time for outputting one layer to 30 seconds;
  • Example 5 is a photograph of the filament of Example 1 set at a condition temperature of 200 ° C., an initial speed of 15 mm / s, an output speed of 110 mm / s, and a time of 20 seconds for outputting a layer of the three-dimensional printer;
  • Example 6 is a photograph of the filament of Example 3 set at a condition temperature of 200 ° C., an initial speed of 15 mm / s, an output speed of 110 mm / s, and a time of outputting one layer of 10 seconds for a three-dimensional printer;
  • Example 7 is a photograph of the filament of Example 4 set at a condition temperature of 200 ° C., an initial speed of 15 mm / s, an output speed of 110 mm / s, and a time of outputting one layer of 10 seconds for a three-dimensional printer;
  • Example 8 is a photograph of the filament of Example 5 set at a condition temperature of 200 ° C., an initial speed of 15 mm / s, an output speed of 110 mm / s, and a time of outputting one layer of 10 seconds for a three-dimensional printer;
  • Example 9 is a photograph of the filament of Example 6 set at a condition temperature of 200 ° C., an initial speed of 15 mm / s, an output speed of 110 mm / s, and a time of 10 seconds of outputting a layer of the three-dimensional printer;
  • Example 10 is a photograph of the filament of Example 7 set at a condition temperature of 200 ° C., an initial speed of 15 mm / s, an output speed of 110 mm / s, and a time of outputting one layer of 10 seconds.
  • the first aspect of the present invention is a polylactic acid composition for a three-dimensional printer filament
  • (iii) discloses a polylactic acid composition for a three-dimensional printer filament comprising at least one selected from the group consisting of 0.01 to 2.0 parts by weight of an additive for the purpose of preventing oxidation.
  • the (A) polylactic acid resin is a polyester-based resin generally produced by ester reaction using lactic acid obtained by decomposing corn starch as a monomer, and the structure thereof is represented by the following Chemical Formula 1.
  • the PLA may be composed of repeating units derived from L-isomer lactic acid, repeating units derived from D-isomer lactic acid, or repeating units derived from L, D-isomer lactic acid, where PLA is L-isomer and D-isomer Repeating units derived from lactic acid can be formed by polymerization (stereo complex PLA or stereo block PLA) alone or in combination (PLLA or PDLA).
  • Table 1 shows the glass transition temperature (Tg), melting temperature (Tm), crystalline structure and enthalpy change of the stereo complex PLA formed in a 50: 50% by weight of L-type PLA (PLLA) of a single component The comparison is shown.
  • the PLLA, PDLA, stereo complex PLA and stereo block PLA may be used alone or in combination.
  • the repeating unit derived from the L-isomer lactic acid is preferably 95% by weight or more, more preferably 97% by weight or more, and most preferably 99% by weight or more.
  • the repeating unit derived from the L-isomer lactic acid is 95 to 100% by weight and the repeating unit derived from the D-isomer lactic acid is 0 to 5% by weight.
  • the PLLA is not particularly limited in molecular weight or molecular weight distribution if the molding process is possible, it is preferable to use a weight average molecular weight of 50,000 or more in terms of the balance of mechanical strength and heat resistance of the molded body, the weight average molecular weight 50,000 ⁇ 300,000 More preferably.
  • the repeating unit derived from the D-isomer lactic acid is preferably 95% by weight or more, more preferably 97% by weight or more, and most preferably 99% by weight or more.
  • the repeating unit derived from the D-isomer lactic acid is 95 to 100% by weight and the repeating unit derived from the L-isomer lactic acid is 0 to 5% by weight.
  • the PDLA is not particularly limited in molecular weight or molecular weight distribution, it is preferable to use a weight average molecular weight of 10,000 or more to increase the crystallization rate, it is more preferable that the weight average molecular weight is 20,000 ⁇ 200,000.
  • the melt index of the polylactic acid is preferably 2 to 15 g / 10 min (210 ° C., 2.16 kg), more preferably 3 to 10 g / 10 min, and most preferably 5 to 10 g / 10 min.
  • the melt index of the PLA is less than 2g / 10min or more than 15g / 10min, impact strength and workability may be reduced.
  • the polylactic acid resin may be included in 95 to 99.9% by weight, preferably 97 to 99.7% by weight.
  • the nucleating agent used in the present invention reduces the crystal size of the polylactic acid resin, serves to improve the three-dimensional printer output speed by reducing the crystallization time due to the increase in crystallinity, is an effective additive for improving the processing productivity.
  • D-type polylactic acid may also play a role as a nucleating agent, but the effect as a nucleating agent according to high resin price and content is lower than the nucleating agent used in the present invention.
  • the nucleating agent is included in an amount of 0.1 to 5% by weight, preferably 0.3 to 3% by weight. When the content of the nucleating agent is less than 0.1% by weight, it may be difficult to exhibit the performance of the nucleating agent. When the content of the nucleating agent is more than 5% by weight, the crystallinity of the resin is increased while the rigidity is increased, and the impact strength is lowered. The physical properties of the resin may not be balanced.
  • nucleating agent examples include talc type nucleating agent, sodium phosphate talc type nucleating agent, phenylorganic zinc phosphate type nucleating agent, phenylorganic zinc phosphate type zinc oxide type nucleating agent and sodium phosphate salt type aromatic aromatic phosphate type calcium salt type nucleating agent It is preferably at least one selected from the group consisting of, and the sodium phosphate salt nucleating agent is, for example, methylenebis (4,6-di-tert-butylphenol) sodium phosphate salt (methylenebis (4,6-di-tert- butylphenol) phosphate sodium salt) may be used.
  • sodium phosphate salt nucleating agent is, for example, methylenebis (4,6-di-tert-butylphenol) sodium phosphate salt (methylenebis (4,6-di-tert- butylphenol) phosphate sodium salt) may be used.
  • the amorphous resin used in the present invention is to improve the mechanical properties such as impact strength while showing an improvement in the crystallization rate in the final resin composition prepared by mixing with the polylactic acid resin.
  • the amorphous resin is not particularly limited, and examples thereof include polycarbonate, acrylonitrile butadiene styrene copolymer, polystyrene, styrene acrylonitrile copolymer, and acrylonitrile.
  • Resin styrene acrylate (acrylonitrile styrene acrylate) copolymer, polymethyl methacrylate (polymethyl methacrylate), polysulfone (polysulfone), polyethersulfone (polyethersulfone), etc. may be used alone or mixed, preferably polycarbonate Resins can be used.
  • melt index (ASTM D1238, 300 ° C., 1.2 kg) of 1-20 g / 10 min, preferably 5-15 g / 10 min, is found to be very advantageous for improving the crystallization rate and mechanical properties. It became.
  • the amorphous resin may be included in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the polylactic acid resin and the nucleating agent, preferably 0.1 to 5 parts by weight, more preferably 1 to 5 parts by weight, most preferably. Preferably it may be included in 2 to 4 parts by weight.
  • the amount of the amorphous resin is less than 0.1 parts by weight of the content may be difficult to expect the effect of improving the crystallization rate is less, when it exceeds 10 parts by weight, the effect of improving the crystallization rate to the supersaturated state is inferior.
  • the polyolefin resin having at least one hydrophilic functional group used in the present invention exhibits an improved crystallization rate but has an appropriate amount of hydrophilic functional group in the polyolefin resin and is applied to the surface in the final resin composition prepared by mixing with the polylactic acid resin.
  • a three-dimensional printer filament characterized by exhibiting excellent paintability by improving adhesion to paint.
  • the polyolefin resin having one or more hydrophilic functional groups may have a hydrophilic functional group content of 0.1 to 10% by weight, and more preferably 0.2 to 3% by weight.
  • a hydrophilic functional group content of 0.1 to 10% by weight, and more preferably 0.2 to 3% by weight.
  • the content of the hydrophilic functional group is less than 0.1% by weight, it may be difficult to obtain an effect of improving colorability, and when the amount of the hydrophilic functional group is more than 10% by weight, compatibility may be reduced due to the aggregation phenomenon of the hydrophilic functional period, thereby decreasing not only the colorability but also the overall physical properties. have.
  • Hydrophilic functional groups for improving such paintability include acrylic, maleic anhydride, amine, carbonyl, hydroxyl, carboxyl and the like.
  • maleic anhydride is preferable for improving the colorability of the final resin composition.
  • the base resin of the polyolefin resin which has the said hydrophilic functional group For example, polyethylene, polypropylene, polybutene, polyisobutylene, polymethylpentene, ethylene and a propylene copolymer, ethylene and butene copolymer, propylene and butene A copolymer, an ethylene vinyl acetate (EVA) resin, or the like may be used alone or in a mixed resin.
  • EVA ethylene vinyl acetate
  • an ethylene vinyl acetate resin may be used.
  • a melt index (ASTM D1238, 190 ° C., 2.16 kg) of 10 to 15 g / 10 min is very advantageous for improving the paintability and impact strength, and also uses maleic anhydride as a hydrophilic functional group.
  • a melt index (ASTM D1238, 190 ° C., 2.16 kg) of 10 to 15 g / 10 min is very advantageous for improving the paintability and impact strength, and also uses maleic anhydride as a hydrophilic functional group.
  • the polyolefin resin having one or more hydrophilic functional groups may be included in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the polylactic acid resin and the nucleating agent, preferably 0.1 to 5 parts by weight, more preferably 1 to 1 part. 5 parts by weight, most preferably 2 to 4 parts by weight.
  • the polyolefin resin content is less than 0.1 parts by weight, it may be difficult to expect the effects of improving the crystallization rate and colorability, and when exceeding 10.0 parts by weight, the effect of improving the crystallization rate is reduced to a supersaturated state.
  • the additive for the purpose of the antioxidant may be used one or more selected from the group consisting of phenolic antioxidant, phosphorus antioxidant or phenol-phosphorus complex antioxidant.
  • the phenolic antioxidant is not particularly limited, but tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane (Tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane) may be preferably used.
  • 3D printers generally use heat to melt the filaments and extrude the melted filaments to produce a product.
  • the filament may be oxidized by a large amount of heat applied when the filament is melted, and thus there is a possibility that the strength of the output produced by the 3D printer may decrease or may not be output normally.
  • the output even if the output is normal, there is a possibility that the output is damaged by being oxidized in contact with the outside air and ultraviolet rays. Therefore, when the oxidation is prevented, the durability of the output is increased, so that the output can be produced with high strength and long shelf life.
  • the additive for the purpose of the antioxidant is included 0.01 to 2.0 parts by weight based on 100 parts by weight of the polylactic acid resin and the nucleating agent in order to exhibit an appropriate antioxidant effect, preferably 0.05 to 1.0 parts by weight, more preferably 0.1 to 0.2 parts by weight may be included.
  • the content of the additive for the purpose of antioxidation is less than 0.01 parts by weight, it may be difficult to exhibit the performance of the additive for the purpose of antioxidation, and when it exceeds 2.0 parts by weight of the resin by the excessive addition of the additive for the purpose of antioxidation A decrease in strength and poor curing of the resin may occur, thereby preventing the balance of physical properties of the resin.
  • the present invention further includes a compatibilizer for good mixing of the (A) polylactic acid resin and (i) amorphous resin, (ii) a polyolefin resin having at least one hydrophilic functional group, or (iii) an additive for the purpose of preventing oxidation.
  • a compatibilizer for good mixing of the (A) polylactic acid resin and (i) amorphous resin, (ii) a polyolefin resin having at least one hydrophilic functional group, or (iii) an additive for the purpose of preventing oxidation.
  • the compatibilizer is a material having the ability to form and stabilize the microphase separation structure by alleviating the difference between the properties of the biodegradable resin and the amorphous resin having a crystal and improve the mechanical properties such as impact strength while maintaining the improved crystallization rate of the final resin composition It may be included in an optimal content for.
  • the compatibilizer content may be included in 0.5 to 10 parts by weight, preferably 1 to 5 parts by weight, based on 100 parts by weight of the total polylactic acid composition.
  • the content of the compatibilizer is less than 0.5 parts by weight, the compatibility with the resin may be weakened and mechanical properties such as impact strength may be lowered.
  • the content of the compatibilizer is greater than 10 parts by weight, it may not be effective in terms of improving physical properties.
  • compatibilizers are particularly limited as long as they can achieve a good mixture of (A) polylactic acid resin, (i) amorphous resin, (ii) polyolefin resin having at least one hydrophilic functional group, or (iii) additive for the purpose of preventing oxidation.
  • A polylactic acid resin
  • amorphous resin polyolefin resin having at least one hydrophilic functional group
  • additive for the purpose of preventing oxidation e.g., a block copolymer compatibilizer or a graft copolymer compatibilizer may be used, preferably a graft copolymer compatibilizer may be used.
  • block copolymer compatibilizer examples include styrene-ethylene / butylene / styrene (SEBS) block copolymers, styrene-ethylene / propylene-styrene (SEPS) block copolymers, methacrylic block copolymers, and polycaprolactone polyester aerials.
  • SEBS styrene-ethylene / butylene / styrene
  • SEPS styrene-ethylene / propylene-styrene
  • methacrylic block copolymers examples include polycaprolactone polyester aerials.
  • graft copolymer compatibilizer examples include polypropylene-maleic anhydride graft copolymer, polyethylene-maleic anhydride graft copolymer, polyethylene-glycidyl methacrylate graft copolymer, and the like. Is a polypropylene-maleic anhydride graft copolymer alone or a polypropylene-maleic anhydride graft copolymer mixed with a polyethylene-maleic anhydride graft copolymer or a polyethylene-glycidyl methacrylate graft copolymer It can be used in one form.
  • the polylactic acid resin composition used for producing a three-dimensional printer filament according to the present invention may further include other additives within the range not departing from the intended use or effect, in addition to the above-described main components.
  • additives for example, thermal stabilizers, light stabilizers, flame retardants, carbon black, antioxidants, impact modifiers and the like can be added to a variety of applications, and other additives, based on 100 parts by weight of the final resin composition excluding additives 0.1 to 10 parts by weight It can be added in the range.
  • the 3D printer filament made of the polylactic acid composition according to the present invention has an improved crystallization speed, which enables a 3D printer output at an extremely high speed, as well as improved heat resistance and mechanical properties when the amorphous resin is mixed. That is, when evaluating the crystallization time using the differential scanning calorimetry (110 °C) it is possible to provide a three-dimensional printer filament of less than 200 seconds.
  • the filament made of the composition to provide a three-dimensional printer filament capable of precise output without any surface transition phenomenon of the resin even at a speed of 110mm / s or more, up to 10 seconds of one-layer output time when printing a three-dimensional printer do.
  • the 'surface transition phenomenon of the resin' refers to a surface appearance by forming a protrusion by forming a protrusion on the surface of the final printed output according to a high output speed when outputting to a 3D printer using a filament made of a polylactic acid composition. It is a phenomenon that is not smooth.
  • the polylactic acid resin composition used for producing a filament for a three-dimensional printer according to the present invention may be prepared by a known melt extrusion method for producing a general resin composition. That is, polylactic acid resin, nucleating agent, amorphous resin, compatibilizer, other additives, etc. may be mixed at the same time and melt-extruded in an extruder to produce a product of a desired form.
  • a second aspect of the present invention relates to a filament for a three-dimensional printer comprising a polylactic acid composition.
  • the above ingredients are first mixed in an appropriate amount.
  • the mixing may be performed by arbitrarily selecting a mixing means well known in the art, such as a tumbler mixer, a blending machine, a hopper, and the like. Thereafter, the homogeneously mixed composition is melt-extruded at 170 to 200 ° C. using a twin screw extruder to be molded into pellets. Then, the resin composition molded into pellets may be extruded into a single screw extruder at 170 to 200 ° C, cooled and wound to be reshaped into a filament having a predetermined diameter, and used for a three-dimensional printer filament.
  • a mixing means well known in the art, such as a tumbler mixer, a blending machine, a hopper, and the like.
  • the homogeneously mixed composition is melt-extruded at 170 to 200 ° C. using a twin screw extruder to be molded into pellets.
  • the resin composition molded into pellets may be extrude
  • the filament molding may be performed by, for example, extruding a screw diameter of 20 to 40 mm and a single screw extruder having a screw length of 100 to 110 mm, and then winding the filament with a diameter of 1.5 to 2 mm using a cooling water tank.
  • PLA product Ingeo 4032D (melt index 7 g / 10 min (210 °C, 2.16 kg)) manufactured by NatureWorks LLC of the United States was used.
  • the amorphous resin product PC-1100 (melt index 10g / 10min (300 degreeC, 1.2 kg)) manufactured by Lotte Chemical Co., Ltd. was used.
  • MPO (Modified Polyolefin) product Adpoly EV-600 (melt index 10-15 g / 10 min (190 ° C., 2.16 kg)) manufactured by Lotte Chemical Co., Ltd. was used.
  • EV-600 is an MPO product having a hydrophilic functional group of maleic anhydride in ethylene vinyl acetate (EVA) series.
  • graft copolymer a polypropylene-maleic anhydride graft copolymer (PH-200, maleic anhydride graft ratio of 3.9%) manufactured by Lotte Chemical Co., Ltd. was used.
  • a pellet was prepared in the same manner as in Example 1, except that 0.3 parts by weight of the nucleating agent KC2000 was mixed in Example 1.
  • a pellet was manufactured in the same manner as in Example 1, except that 3 parts by weight of amorphous resin PC-1100 was further mixed in Example 1.
  • a pellet was manufactured in the same manner as in Example 1, except that 3 parts by weight of an ethylene vinyl acetate (EVA) series EV-600 having a hydrophilic functional group of maleic anhydride was further mixed.
  • EVA ethylene vinyl acetate
  • a pellet was prepared in the same manner as in Example 1, except that 3 parts by weight of PC-1100 and 3 parts by weight of EV-600 were further mixed in Example 1.
  • pellets were prepared in the same manner as in Example 1.
  • Example 1 The pellets produced in Example 1 were extruded with a single screw extruder at 170 to 200 ° C., cooled and wound to prepare a filament having a constant diameter of 1.75 mm.
  • Example 3 The pellet produced in Example 3 was extruded with a single screw extruder at 170 to 200 ° C., cooled and wound to prepare a filament having a constant diameter of 1.75 mm.
  • Example 4 The pellet produced in Example 4 was extruded with a single screw extruder at 170 to 200 ° C., cooled and wound to prepare a filament having a constant diameter of 1.75 mm.
  • Example 5 The pellets produced in Example 5 were extruded by a single screw extruder at 170 to 200 ° C., cooled and wound to prepare a filament having a constant diameter of 1.75 mm.
  • Example 6 The pellet produced in Example 6 was extruded with a single screw extruder at 170 to 200 ° C. to cool and wind to prepare a filament having a constant diameter of 1.75 mm.
  • Example 7 The pellet produced in Example 7 was extruded with a single screw extruder at 170 to 200 ° C. to cool and wind to prepare a filament having a constant diameter of 1.75 mm.
  • a pellet was prepared in the same manner as in Example 1, except that the polylactic acid resin and the antioxidant were used without adding the nucleating agent in Example 1. Extruded pellets were dried for 12 hours at 80 °C extruded by a single screw extruder of 170 ⁇ 200 °C cooled and wound to prepare a filament having a constant diameter 1.75 mm.
  • Polylactic acid filament MW10 Natural
  • Canon Korea Polylactic acid filament MW10 (Natural) manufactured by Canon Korea was used.
  • DSC Differential scanning calorimetry
  • DSC Q200 Differential scanning calorimetry (DSC Q200, TA Instrument) of the resin composition prepared according to Examples 1 to 7 and Comparative Example 1 to evaluate the crystallization rate of the three-dimensional printer filament according to the present invention )
  • DSC Q200 Differential scanning calorimetry equipment
  • the temperature was increased from 30 ° C. to 250 ° C. at a rate of 20 ° C./min, quenched at a rate of 80 ° C./min, and the results of measurement of crystallization time at 110 ° C. were shown in FIG. 2. .
  • a nucleating agent 0.3 to 3 parts by weight of a nucleating agent is mixed with at least one selected from the group consisting of (i) an amorphous resin, (ii) a polyolefin resin having at least one hydrophilic functional group, and (iii) an antioxidant It was found that the crystallization rate was improved by about 80% or more compared to the polylactic acid composition to which no nucleating agent was added.
  • the filament prepared according to Examples 8 to 13 and Comparative Example 2 filament was evaluated by the output speed for each output speed.
  • the 3D printer used MARV manufactured by Canon Korea.
  • To compare the output performance use the filament of Comparative Example 2 to adjust the temperature of the three-dimensional printer to 200 ° C, the initial speed of 15 mm / s, the output speed of 40 or 110 mm / s, and the time of printing one layer from 10 to 30 seconds.
  • the condition temperature of the three-dimensional printer was 200 ° C., an initial speed of 15 mm / s, an output speed of 110 mm / s, and one layer.
  • the output time was set to 10 seconds and outputted using the same drawing, and the results are shown in FIGS. 3 to 10.
  • Comparative Example 2 The time taken to output FIG. 3 using the filament was about 10 hours and the time taken to output FIGS. 5 to 10 using the filaments of Examples 8 to 13 was about 2 hours. Referring to FIGS. 3 to 4, as the speed increases, the output performance of the filament using Comparative Example 2 drops sharply, while the output time of the filaments of Examples 8 to 13 shown in FIGS. could be maintained. That is, when the filament of Comparative Example 2 was used, the surface transition phenomenon of the resin occurred, and thus the surface of the structure was not uniform (FIGS. 3 and 4). However, when the filaments of Examples 8 to 13 were used, It was confirmed that the transition phenomenon of the resin did not occur on the surface, indicating a very even surface (FIGS. 5 to 10).

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention porte sur une composition d'acide polylactique pour un filament d'imprimante tridimensionnelle, contenant, dans de l'acide polylactique, un agent de nucléation ayant une composition spécifique, et une résine non cristalline ou une résine de polyoléfine ayant un ou plusieurs groupes fonctionnels hydrophiles de façon à augmenter le taux de cristallisation d'une résine, contribuant ainsi à l'amélioration de la vitesse d'impression d'une imprimante tridimensionnelle. La présente invention concerne une composition d'acide polylactique pour un filament d'imprimante tridimensionnelle, comprenant : (A) 95 à 99,9 % en poids d'un acide polylactique ; (B) 0,1 à 5 % en poids d'un agent de nucléation ; et, par rapport à 100 parties en poids de (A) l'acide polylactique et (B) l'agent de nucléation, l'un quelconque ou plusieurs éléments choisis dans le groupe constitué de (i) 0,1 à 10,0 parties en poids d'une résine non cristalline, (ii) 0,1 à 10 parties en poids d'une résine de polyoléfine ayant un ou plusieurs groupes fonctionnels hydrophiles et (iii) 0,01 à 2,0 parties en poids d'un additif pour empêcher l'oxydation.
PCT/KR2017/007162 2016-07-05 2017-07-05 Composition d'acide polylactique pour filament d'imprimante tridimensionnelle, ayant une vitesse d'impression améliorée WO2018008969A1 (fr)

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KR1020160084794A KR101812884B1 (ko) 2016-07-05 2016-07-05 출력 속도가 향상된 3차원 프린터 필라멘트용 폴리유산 조성물
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CN116421778A (zh) * 2023-03-22 2023-07-14 大连工业大学 一种取向结构的3d打印支架材料及其制备方法

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