KR20200071817A - 3-dimension printer polylactic acid filament eggshell composition which has excellent heat resistance and mechanical property and filament for 3-dimension printer using the same - Google Patents

Abstract

Disclosed are: a polylactic acid resin composition for a 3D printer filament which can increase mechanical strength and a crystallization rate of a polylactic acid resin, and contributes to an increase in a 3D printer output speed; and a filament for a 3D printer manufactured using the same. The present invention provides the polylactic acid resin composition for a 3D printer filament, comprising: (A) 90.0 to 99.9 wt% of a polylactic acid resin; and (B) 0.1 to 10.0 wt% of an eggshell, and the filament for a 3D printer manufactured using the same.

Description

Polylactic acid resin composition for 3D printer filaments having excellent heat resistance and mechanical properties and filaments for 3D printers using the same{3-DIMENSION PRINTER POLYLACTIC ACID FILAMENT EGGSHELL COMPOSITION WHICH HAS EXCELLENT HEAT RESISTANCE AND MECHANICAL PROPERTY AND FILAMENT FOR 3-DIMENSION PRINTER USING THE SAME}

The present invention relates to a polylactic acid resin composition and a filament for a 3D printer using the same, and more particularly, to a polylactic acid resin composition for a 3D printer filament having excellent heat resistance and mechanical properties and a filament for a 3D printer using the same.

A three-dimensional (3-Dimension) printer is a device that produces three-dimensional objects while sequentially stacking layers of fine materials by sequentially spraying ink of a special material. 3D printing is spreading in various fields. In addition to the automotive sector, which consists of many parts, it is used by many manufacturers for the purpose of making various models such as medical human models, household products such as toothbrushes and razor.

Currently, the most commonly used material for 3D printing is a photo-curable polymer material'photopolymer' that hardens when it receives light. This accounts for 56% of the total market. The next most popular material is a solid, thermoplastic, free-melting and solidified plastic that occupies 40% of the market, and metal powder is expected to gradually increase in the future. The form of the thermoplastic material may have a filament, particle or powder form. Filament type 3D printing is faster than other types in terms of speed, so productivity is high and diffusion speed is fast.

Meanwhile, in recent years, efforts to reduce greenhouse gases due to global warming have been extensively conducted, and as one of those efforts, development of biodegradable polymer materials that decompose in nature has attracted attention. Most existing polymers use petroleum resources as a basic raw material, but this is likely to be depleted in the future, and carbon dioxide generated by consuming large amounts of petroleum resources is recognized as a major cause of global warming. Therefore, attention has been focused on the development and industrial application of biodegradable polymers using plant resources that grow using carbon dioxide from the atmosphere. In particular, the application of biodegradable polymer materials such as polylactic acid (PLA) as a three-dimensional printer filament material is also becoming active.

However, polylactic acid has a characteristic of a slow crystallization rate, and thus has a limitation in that a 3D printing speed is slow. Currently commercially available polylactic acid filament takes about 10 hours based on about 35 g of output and size of 70 x 61 x 64 mm, which is very inconvenient to print.

Looking at the related prior literature, Publication No. 2012-0108798 is an L-type and D-type polylactic acid stereocomposite which improves the crystallization rate through heating after heating the mold cavity surface to 100-110°C, and preserves the stereocomplex crystal For this purpose, it discloses a technique that uses a melting temperature of 190 to 195°C, but its use is limited to automotive materials and is not mentioned in the application of filaments for 3D printers. Becomes.

In addition, Patent Publication No. 2012-0129500 discloses a polylactic acid composition having improved mechanical properties and crystallization speed by applying phyllite powder and carbon nanotubes which are organically surface-treated to polylactic acid, as a nucleating agent for improving crystallization rate. Although mention is made of phyllite powder and carbon nanotubes, it is not suitable as a material for a 3D printer that requires various colors by using carbon nanotubes.

In addition, Korean Patent Publication No. 2012-0022420 relates to a method for manufacturing heat-resistant polylactic acid fibers obtained by mixing L-type polylactic acid, D-type polylactic acid, and polyester, and converting heat-resistant polylactic acid stereocomplex into fibers through high-temperature heat treatment. Although the application method is disclosed, the use is limited to stretched fibers and is not mentioned in the application of filaments for 3D printers, and the cost burden is a problem by using D-type polylactic acid.

Therefore, the present invention was devised to solve the above problems, it is possible to increase the mechanical strength and crystallization rate of the polylactic acid resin, and the polylactic acid resin composition for a 3D printer filament contributing to an increase in the 3D printer output speed and the same It is intended to provide a filament for a three-dimensional printer manufactured using.

In order to solve the above problems, the present invention, (A) polylactic acid resin 90.0 ~ 99.9% by weight; And (B) eggshell 0.1 ~ 10.0% by weight; provides a polylactic acid resin composition for a three-dimensional printer filament comprising a.

In addition, the polylactic acid resin is selected from the group consisting of poly-L-lactic acid (PLLA), poly-D-lactic acid (PDLA), stereo complex polylactic acid (Stereo complex PLA) and stereo block polylactic acid (Stereo block PLA). It provides a polylactic acid resin composition for a three-dimensional printer filament, characterized in that at least one.

In addition, the egg shell provides a polylactic acid resin composition for a three-dimensional printer filament, characterized in that the powder produced by the firing method.

In addition, (A) the polylactic acid resin and (B) 100 parts by weight of the egg shell total, (C) 0.1 to 10.0 parts by weight of the amorphous resin or (D) 0.1 to 10.0 parts of the polyolefin resin having one or more hydrophilic functional groups part; And it provides a polylactic acid resin composition for a three-dimensional printer filament further comprising; 0.1 to 10 parts by weight of a compatibilizer comprising a block copolymer or a graft copolymer.

In addition, the amorphous resin is polycarbonate (polycarbonate), acrylonitrile butadiene styrene (acrylonitrile butadiene styrene) copolymer, polystyrene (polystyrene), styrene acrylonitrile (styrene acrylonitrile) copolymer, acrylonitrile styrene acrylate (acrylonitrile acrylate) Polylactic acid resin composition for three-dimensional printer filaments, characterized by at least one selected from the group consisting of styrene acrylate copolymers, polymethyl methacrylate, polysulfone, and polyethersulfone Gives

In addition, the polyolefin resin having one or more hydrophilic functional groups has a content of 0.1 to 10% by weight of the hydrophilic functional groups, and the hydrophilic functional groups are acrylic, maleic anhydride, amine, and carbonyl. It provides a polylactic acid resin composition for a three-dimensional printer filament, characterized in that it is selected from the group consisting of (carbonyl), hydroxyl (hydroxyl) and carboxyl (carboxyl).

In addition, the polyolefin resin having a maleic anhydride as the hydrophilic functional group, characterized in that the melt index (ASTM D 1238, 190 ℃, 2.16 ㎏) is an ethylene vinyl acetate (EVA) resin 10-15 g/10min A polylactic acid resin composition for dimensional printer filaments.

In addition, the block copolymer is a styrene-ethylene/butylene/styrene (SEBS) block copolymer, a styrene-ethylene/propylene-styrene (SEPS) block copolymer, a methacrylic block copolymer, a polycaprolactone polyester copolymer , Polycaprolactone polyester/poly(tetramethylene glycol) block polyol copolymer and at least one selected from the group consisting of methacrylate polystyrene copolymers, wherein the graft copolymer is polypropylene-maleic anhydride graft copolymer It provides a polylactic acid resin composition for a three-dimensional printer filament, characterized in that at least one member selected from the group consisting of coalescence, polyethylene-maleic anhydride graft copolymer and polyethylene-glycidyl methacrylate graft copolymer.

In addition, the polylactic acid resin composition for a three-dimensional printer filament provides a polylactic acid resin composition for a three-dimensional printer filament, characterized in that it is 200 seconds or less when evaluating crystallization time using differential scanning calorimetry (110°C).

In addition, the polylactic acid resin composition for a three-dimensional printer filament is characterized in that the heat deflection temperature (ASTM D648, 4.6 kgf/cm 2) is 100°C or higher, and the IZOD impact strength (ASTM D256, 23°C) is 4 kgfcm/cm or higher. It provides a polylactic acid resin composition for a three-dimensional printer filament.

In order to solve the above another problem, the present invention provides a filament for a three-dimensional printer comprising the resin composition.

In addition, the filament provides a filament for a three-dimensional printer, characterized in that the surface migration phenomenon of the resin does not occur when output under the following conditions.

[Output condition]

Using the filament, 35 g of output was output to a 3D printer set at a nozzle temperature of 200°C, an output speed of 110 mm/s, and a layer printing time of 10 seconds.

According to the present invention, a polylactic acid resin composition for improving the crystallization speed by mixing a certain amount of eggshell with a polynucleic acid resin as a natural nucleating agent and having excellent mechanical properties is obtained. Can provide.

Hereinafter, preferred embodiments of the present invention will be described in detail. In the description of the present invention, when it is determined that a detailed description of related known technologies may obscure the subject matter of the present invention, the detailed description will be omitted. Throughout the specification, when a part “includes” a certain component, this means that other components may be further included rather than excluding other components, unless otherwise stated.

The present inventors watched the problem of crystallization rate of polylactic acid, which is the main cause of the slow 3D printer output speed in filaments for 3D printers using polylactic acid resins, and repeatedly studied them to solve them. When the egg shell is mixed with a specific content as a nucleating agent, it has been found that the crystallization rate is improved and the mechanical properties are excellent, leading to the present invention.

Therefore, the present invention (A) polylactic acid resin 90.0 ~ 99.9% by weight; And (B) eggshell 0.1 ~ 10.0% by weight; discloses a polylactic acid resin composition for a three-dimensional printer filament comprising a.

In the present invention, the (A) polylactic acid resin is a polyester resin made by an ester reaction using a lactic acid obtained by decomposing corn starch as a monomer, and its structure is as shown in Chemical Formula 1.

[Formula 1]

The PLA may be composed of repeat units derived from L-isomer heritage, repeat units derived from D-isomer heritage, or L, repeat units derived from D-isomer heritage, PLA is L-isomer and D-isomer It can be formed by polymerization (stereo complex PLA or stereo block PLA) of a repeating unit derived from lactic acid alone (PLLA or PDLA) or in combination. Table 1 below shows the changes in glass transition temperature (Tg), melting temperature (Tm), crystalline structure and melting enthalpy of stereocomplex PLA formed with a single component of L-type PLA (PLLA) at a ratio of 50:50% by weight. It is shown by comparison.

When using PLA as a biodegradable polyester resin in the present invention, the PLLA, PDLA, stereo complex PLA and stereo block PLA can be used alone or in combination.

In the case of using the PLLA, it is preferable that the repeating unit derived from L-isomer lactic acid is 95% by weight or more, more preferably 97% by weight or more, and most preferably 99% by weight or more in terms of the balance of heat resistance and moldability. At this time, when the hydrolysis resistance is further considered, it is more preferable that the repeating units derived from L-isomer lactic acid are 95 to 100% by weight and the repeating units derived from D-isomer lactic acid are 0 to 5% by weight.

In addition, the PLLA has no particular limitation on molecular weight or molecular weight distribution if molding is possible, but 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, and the weight average molecular weight is 50,000 to 300,000. It is more preferable.

In the case of using the PDLA, it is preferable that the repeating unit derived from the D-isomer lactic acid is 95% by weight or more, more preferably 97% by weight or more, and most preferably 99% by weight or more in terms of balance of heat resistance and moldability. At this time, further considering the hydrolysis resistance, it is more preferable that the repeating unit derived from the D-isomeric lactic acid is 95 to 100% by weight and the repeating unit derived from the L-isomeric lactic acid is 0 to 5% by weight.

In addition, the PDLA has no particular limitation on molecular weight or molecular weight distribution, but it is preferable to use a weight average molecular weight of 10,000 or more in order to increase the crystallization rate, and it is more preferable that the weight average molecular weight is 20,000 to 200,000.

The content of the polylactic acid resin is included in a content of 90.0 to 99.9% by weight in consideration of the egg shell content to be described later, preferably 92 to 99.9% by weight, and more preferably 95 to 99.9% by weight.

In the present invention, the melt index (210° C., 2.16 kg load) of the polylactic acid resin is preferably 2 to 15 g/10min, more preferably 3 to 10 g/10min, and 5 to 10 g/10min. Most preferred. When the PLA melt index is less than 2 g/10min or more than 15 g/10min, impact strength and workability may be deteriorated.

In the present invention, an egg shell is used as a nucleating agent for natural materials to improve crystallization speed and mechanical properties as a polylactic acid resin for application to a 3D printer filament.

The egg shell is an effective additive to improve the processing productivity by reducing the crystal size of the polylactic acid resin and reducing the crystallization time according to the increase in crystallinity, thereby improving the 3D printer output speed.

D-type polylactic acid may also play a role as a nucleating agent, but its effect as a nucleating agent according to the high resin price and content is lower than the egg shell used in the present invention. The egg shell is included in an amount of 0.1 to 10% by weight, preferably 0.1 to 8% by weight, and more preferably 0.1 to 5% by weight in order to exhibit an appropriate crystallization rate. When the egg shell content is less than 0.1% by weight, it may be difficult to exert the performance as a nucleating agent, and when it exceeds 10% by weight, the crystallinity of the resin increases and the stiffness increases, resulting in a decrease in impact strength. The balance of physical properties may not be achieved.

The eggshell may include the outer shell or the outer shell of the plasma membrane that is discarded after using egg whites and egg yolk as eggs of animals such as eggs, and is not particularly limited to the shape or size of the eggshell used in the present invention. , It may be used, preferably in the form of powder produced by the firing method.

In the present invention, in order to improve mechanical properties such as impact strength while showing an increase in crystallization rate in the final resin composition prepared by mixing with the polylactic acid resin, it may further include (C) amorphous resin.

The amorphous resin is not particularly limited, for example, 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), etc. can be used alone or mixed resin, preferably polycarbonate Resin can be used. At this time, when a polycarbonate resin is used, the melt index (ASTM D1238, 300°C, 1.2 kg) is 1 to 20 g/10min, preferably 5 to 15 g/10min, which is very advantageous for improving mechanical properties and improving the crystallization rate. Was confirmed.

Meanwhile, in the present invention, the amorphous resin may be included in an amount of 0.1 to 10 parts by weight, preferably 1 to 5 parts by weight based on 100 parts by weight of the (A) polylactic acid resin and (B) egg shells. It can be included as When the content of the amorphous resin is less than 0.1 parts by weight, the content may be small, so it may be difficult to expect an effect of improving the crystallization rate, and when it exceeds 10 parts by weight, the effect of improving the crystallization rate in a supersaturated state is poor.

In the present invention, (D) may further include a polyolefin resin having one or more hydrophilic functional groups. The polyolefin resin having one or more hydrophilic functional groups exhibits an improvement in crystallization rate, but has an appropriate amount of hydrophilic functional groups in the polyolefin resin, thereby adhering with the coating applied to the surface in the final resin composition prepared by mixing with the polylactic acid resin. By improving the properties, it is possible to exhibit excellent paintability.

Meanwhile, the polyolefin resin having one or more hydrophilic functional groups preferably has a hydrophilic functional group content of 0.1 to 10% by weight, more preferably 0.2 to 3% by weight. When the content of the hydrophilic functional group is less than 0.1% by weight, it may be difficult to obtain an effect of improving paintability, and when it exceeds 10% by weight, compatibility may be lowered due to aggravation of the hydrophilic action period, and thus, not only paintability but also physical properties may be reduced. have.

Examples of the hydrophilic functional groups that improve the paintability include acrylic, maleic anhydride, amine, carbonyl, hydroxyl, and carboxyl. In particular, when maleic anhydride is used, it is preferable to improve the paintability of the final resin composition.

The base resin of the polyolefin resin having a hydrophilic functional group is not particularly limited, for example, polyethylene, polypropylene, polybutene, polyisobutylene, polymethylpentene, ethylene and propylene copolymer, ethylene and butene copolymer, propylene and butene Copolymers, ethylene vinyl acetate (EVA) resins, etc. may be used alone or mixed resins, preferably ethylene vinyl acetate resins. At this time, when ethylene vinyl acetate resin is used, the melt index (ASTM D1238, 190°C, 2.16 kg) of 10 to 15 g/10min is very advantageous for improving paint strength and impact strength, and also maleic anhydride as a hydrophilic functional group. When it was included in the preferred content, it was confirmed that the degree of improvement in the paintability of the final resin composition can be maximized.

Meanwhile, in the present invention, 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 (A) polylactic acid resin and (B) egg shells, and preferably 1 to 5 parts by weight may be included. When the content of the polyolefin resin is less than 0.1 parts by weight, it may be difficult to expect an effect of improving crystallization rate and improving paintability, and when it exceeds 10 parts by weight, the effect of improving crystallization rate in a supersaturated state is poor.

In the present invention, a compatibilizer for good mixing of (A) the polylactic acid resin and (C) the amorphous resin or (D) the polyolefin resin having one or more hydrophilic functional groups may be further included. The compatibilizer is a material having the ability to form and stabilize a microphase separation structure by alleviating differences in properties between a biodegradable resin having crystals and an amorphous resin, and improving mechanical properties such as impact strength while maintaining an improved crystallization rate of the final resin composition. For optimal content, it can be included. To this end, the compatibilizer content may be included in 0.1 to 10 parts by weight based on 100 parts by weight of the (A) polylactic acid resin and (B) egg shell, and preferably 1 to 5 parts by weight. When the compatibilizer content is less than 0.1 parts by weight, the compatibility with the resin is weakened, and mechanical properties such as impact strength may be deteriorated.

The compatibilizer is not particularly limited as long as it can achieve good mixing of (A) the polylactic acid resin and (C) the amorphous resin or (D) the polyolefin resin having one or more hydrophilic functional groups, for example, a block copolymer compatibilizer or A graft copolymer compatibilizer can be used, preferably a graft copolymer compatibilizer can be used.

Examples of the block copolymer compatibilizer include styrene-ethylene/butylene/styrene (SEBS) block copolymers, styrene-ethylene/propylene-styrene (SEPS) block copolymers, methacrylic block copolymers, and polycaprolactone polyester copolymers. Copolymers, polycaprolactone polyester/poly(tetramethylene glycol) block polyol copolymers, methacrylate polystyrene copolymers, and the like, preferably styrene-ethylene/butylene/styrene (SEBS) block copolymers, styrene Ethylene/propylene-styrene (SEPS) block copolymers can be used.

Examples of the graft copolymer compatibilizer 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 or 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 in the manufacture of a filament for a 3D printer according to the present invention may further include other additives within a range not departing from its intended use or effect, in addition to the above-mentioned main components. For example, heat stabilizers, light stabilizers, flame retardants, carbon black, antioxidants, impact modifiers, etc. may be additionally added to be used for various purposes, wherein other additives are 0.1 to 10 weights based on 100 parts by weight of the final resin composition excluding additives. It can be added in a sub range.

The polylactic acid resin composition for a three-dimensional printer filament according to the present invention has an improved crystallization speed, which enables not only a three-dimensional printer output at an extremely high speed, but also improves heat resistance and improves mechanical properties when mixing an amorphous resin. That is, it is possible to provide a resin composition for a three-dimensional printer filament that is 200 seconds or less, preferably 180 seconds or less, and more preferably 160 seconds or less when evaluating crystallization time using differential scanning calorimetry (110° C.).

In addition, the polylactic acid resin composition for a three-dimensional printer filament according to the present invention improves heat resistance while maintaining good impact resistance. That is, the thermal strain temperature (ASTM D648, 4.6 kgf/cm 2) is 100°C or higher, preferably 110°C or higher, and the IZOD impact strength (ASTM D256, 23°C) is 4 kgfcm/cm or higher, preferably 5 to It is possible to provide a polylactic acid resin composition for 3D printer filaments of 50 kgfcm/cm.

In addition, it is possible to provide a polylactic acid resin composition for a three-dimensional printer filament in which a surface migration phenomenon of a resin does not occur when the filament manufactured using the polylactic acid resin composition is output under the following conditions.

[Output condition]

Using the filament, 35 g of output was output to a 3D printer set at a nozzle temperature of 200°C, an output speed of 110 mm/s, and a layer printing time of 10 seconds.

The filament for a 3D printer according to the present invention can be produced by a known melt extrusion method for producing a general resin composition. That is, polylactic acid resin, egg shell, antioxidant, and other additives can be simultaneously mixed and then melt-extruded in an extruder to produce a desired product.

For example, the ingredients are first mixed in an appropriate amount. At this time, mixing may be performed by arbitrarily selecting mixing means well known in the art to which the present invention pertains, such as tumbler mixer, blending machine, hopper, and the like. Thereafter, the homogeneously mixed composition is melt-extruded at 170 to 200°C using a twin-screw extruder and molded into pellets. Thereafter, the resin composition molded into pellets is extruded by a single-screw extruder at 170 to 200°C, cooled and wound up, and re-molded into filaments having a certain diameter, and thus can be used for 3D printer filaments. The filament molding may be performed, for example, by extruding with a uniaxial extruder having a screw diameter of 20 to 40 mm and a screw length of 100 to 110 mm, cooling using a cooling water tank, and then winding through filaments having a diameter of 1.5 to 2 mm.

Hereinafter, a specific embodiment according to the present invention will be described.

First, the specifications of the components used in Examples and Comparative Examples of the present invention are as follows.

(1) Polylactic acid resin

The PLA product Ingeo 4032D (melting index (210° C., 2.16 kg load) 7 g/10min) manufactured by NatureWorks LLC was used.

(2) nucleating agents

As a nucleating agent for natural materials, egg shell calcium products (NEC40, average particle size 6 to 10 μm) manufactured by Sejin F&G (Korea) were used.

As a commercial nucleating agent other than egg shell, a nucleating agent product KC2000 manufactured by KOCH Korea, a nuclear product NA-902 manufactured by ADEKA, Japan, and HPN-20E manufactured by Milliken, USA were used.

(3) amorphous resin

The amorphous resin product PC-1100 (melting index (300°C, 1.2 kg load) 10 g/10min) manufactured by Lotte Chemical Co., Ltd. was used.

(4) Polyolefin resin having one or more hydrophilic functional groups

Adpoly EV-600 (melting index (190°C, 2.16 kg load) 10-15 g/10min) manufactured by MPO (Modified Polyolefin) manufactured by Lotte Chemical Co., Ltd. was used. EV-600 is an MPO product that has a hydrophilic functional group of maleic anhydride in ethylene vinyl acetate (EVA) series.

(5) Compatibilizer

As a graft copolymer, a polypropylene-maleic anhydride graft copolymer (PH-200, maleic anhydride graft ratio 3.9% by weight) manufactured by Lotte Chemical Co., Ltd. was used.

(6) Phenolic antioxidant

In order to prevent the thermal decomposition of the resin composition, Songnox®1010 manufactured by Songwon Industry in Korea was used.

Example 1

99.7 parts by weight of polylactic acid resin, 0.3 parts by weight of natural nucleating agent eggshell and 0.1 phr of phenolic antioxidant (0.1 parts by weight based on 100 parts by weight of total components without additives) were mixed for 5 minutes using a tumbler mixer and L/D After extruding at a temperature range of 170 to 200°C in a twin-screw extruder having a diameter of 40 mm and 40 mm, the extrudate was prepared in pellet form. The extruded pellets were dried at 80° C. for 12 hours.

Examples 2 to 4 and Comparative Examples 1 to 4

Pellets were prepared in the same manner as in Example 1, except that each component in Example 1 was mixed by adjusting the composition (unit: parts by weight) shown in Table 2 below.

Comparative Example 5

A polylactic acid filament MW10 (Natural) manufactured by Canon Korea was prepared.

Test Example 1

Differential scanning calorimetry (DSC) equipment for the resin compositions prepared according to Examples 1 to 4 and Comparative Examples 1 to 4 for evaluation of the crystallization rate improvement of the polylactic acid resin composition for 3D printer filaments according to the present invention It was measured under nitrogen using (DSC Q200, TA Instrument), the temperature was raised from 30°C to 250°C at a rate of 20°C/min for each specimen, and then rapidly cooled at a rate of 80°C/min and the crystallization time was measured at 110°C. The results are shown in Table 3 below.

Referring to Table 3, when a certain amount of eggshell is mixed with a polynucleic acid resin as a natural nucleating agent according to the present invention (Examples 1 and 2), superior crystallization rate characteristics compared to when no nucleating agent is used (Comparative Example 1) It is shown that it shows a significantly improved crystallization rate even when a commercial nucleating agent is used (Comparative Examples 2 to 4).

Furthermore, when the polyolefin resin having a specific one or more hydrophilic functional groups is additionally mixed and used as an additive resin together with the natural material nucleating agent shell (Example 4), the crystallization rate is further improved, and in particular, a specific amorphous resin is added as an additive resin. When used in combination (Example 3), it can be seen that the crystallization rate is significantly improved.

Test Example 2

To evaluate the three-dimensional output performance of the filament for a three-dimensional printer according to the present invention, the pellets prepared according to Examples 1 and 3 were extruded by a single-screw extruder of 170 to 200°C, cooled and wound up to have a constant diameter of 1.75 mm A filament was prepared, and the output performance of the produced filament and the filament of Comparative Example 5 was evaluated using a 3D printer. The 3D printer used MARV manufactured by Canon Korea. For comparison of the output performance, using the filaments prepared according to Examples 1 and 3 and Comparative Example 5, the condition temperature of the 3D printer was 200°C, the initial speed of 15 mm/s, the output speed of 110 mm/s, and one layer was output. The time was set to 10 seconds and output was made using an output drawing of about 35 g, and the results are shown in Table 4 below.

Referring to Table 4, it can be seen that when a certain amount of eggshell is mixed with a polynucleic acid resin as a natural nucleating agent according to the present invention (Example 1), the output performance is significantly improved compared to a conventional commercial product (Comparative Example 5). It can be seen that when the specific specific amorphous resin is additionally mixed and used as an additive resin together with the nucleating agent eggshell of the material (Example 3), the output performance is further improved.

Test Example 3

In order to evaluate the physical properties of the filament for a three-dimensional printer according to the present invention, the resin compositions prepared according to Examples 1, 3 and 4 and Comparative Examples 1 to 3 have an injection machine having a clamping force of 150 tons (Dongshin Hydraulic, Korea) (injection temperature After cooling for 80 seconds at 180~200℃, extracting the molded article using the ASTM test piece to prepare a physical property specimen, and the thermal deformation temperature (ASTM D648, 4.6 kgf/㎠) and IZOD impact strength (ASTM) D256, 23°C) and the results are shown in Table 5 below.

Referring to Table 5, when mixing a certain amount of eggshell as a natural material nucleating agent in the polylactic acid resin according to the present invention (Example 1) heat resistance compared to when the nucleating agent is not used (Comparative Example 1) while maintaining good impact resistance It can be seen that the properties are significantly improved, and the heat resistance properties are considerably improved even when a commercial nucleating agent is used (Comparative Examples 2 and 3).

Furthermore, when the polyolefin resin having a specific one or more hydrophilic functional groups is additionally mixed and used as an additive resin together with the natural nucleating agent egg shell (Example 4), the heat resistance properties are further improved, and in particular, a specific amorphous resin is added as an additive resin. In the case of mixing and using (Example 3), it can be seen that the heat resistance properties are significantly improved.

The preferred embodiments of the present invention have been described above in detail. The description of the present invention is for illustration only, and those skilled in the art to which the present invention pertains will appreciate that other specific forms can be easily modified without changing the technical spirit or essential features of the present invention.

Therefore, the scope of the present invention is indicated by the claims, which will be described later, rather than by the detailed description, and all the changed or modified forms derived from the meaning, scope, and equivalent concepts of the claims are included in the scope of the present invention. Should be interpreted.

Claims (12)

(A) 90.0 to 99.9% by weight of polylactic acid resin; And (B) 0.1 to 10.0% by weight of eggshell; a polylactic acid resin composition for a three-dimensional printer filament. According to claim 1,
The polylactic acid resin is selected from the group consisting of poly-L-lactic acid (PLLA), poly-D-lactic acid (PDLA), stereo complex polylactic acid (Stereo complex PLA) and stereo block polylactic acid (Stereo block PLA). Polylactic acid resin composition for a three-dimensional printer filament, characterized in that the above. According to claim 1,
The egg shell is a polylactic acid resin composition for a three-dimensional printer filament, characterized in that the powder produced by the firing method. According to claim 1,
(A) 0.1 to 10.0 parts by weight of the amorphous resin or (D) 0.1 to 10.0 parts by weight of the polyolefin resin having one or more hydrophilic functional groups with respect to the (A) polylactic acid resin and the total of 100 parts by weight of the (B) egg shell; And 0.1 to 10 parts by weight of a compatibilizer comprising a block copolymer or a graft copolymer; polylactic acid resin composition for a three-dimensional printer filaments further comprising. According to claim 4,
The amorphous resin is polycarbonate, acrylonitrile butadiene styrene copolymer, polystyrene, styrene acrylonitrile copolymer, acrylonitrile styrene acrylate ) Copolymer, polymethyl methacrylate (polymethyl methacrylate), polysulfone (polysulfone) and polyethersulfone (polyethersulfone) at least one selected from the group consisting of polylactic acid resin composition for a three-dimensional printer filament. According to claim 4,
The polyolefin resin having one or more hydrophilic functional groups has a content of 0.1 to 10% by weight of the hydrophilic functional groups, and the hydrophilic functional groups are acrylic, maleic anhydride, amine, and carbonyl. ), hydroxyl (hydroxyl) and carboxyl (carboxyl) polylactic acid resin composition for a three-dimensional printer filament, characterized in that selected from the group consisting of. The method of claim 6,
The polyolefin resin has a maleic anhydride as the hydrophilic functional group, a three-dimensional printer, characterized in that the ethylene vinyl acetate (EVA) resin having a melt index (ASTM D 1238, 190°C, 2.16 kg) of 10 to 15 g/10min. Polylactic acid resin composition for filament. According to claim 4,
The block copolymer is a styrene-ethylene/butylene/styrene (SEBS) block copolymer, a styrene-ethylene/propylene-styrene (SEPS) block copolymer, a methacrylic block copolymer, a polycaprolactone polyester copolymer, poly One or more selected from the group consisting of caprolactone polyester/poly(tetramethylene glycol) block polyol copolymer and methacrylate polystyrene copolymer, wherein the graft copolymer is a polypropylene-maleic anhydride graft copolymer, Polyethylene-maleic anhydride graft copolymer and polyethylene-glycidyl methacrylate graft copolymer is a polylactic acid resin composition for a three-dimensional printer filament, characterized in that at least one member selected from the group consisting of. The method according to any one of claims 1 to 8,
The polylactic acid resin composition for a three-dimensional printer filament is a polylactic acid resin composition for a three-dimensional printer filament, characterized in that 200 seconds or less when evaluating crystallization time using differential scanning calorimetry (110°C). The method according to any one of claims 1 to 8,
The polylactic acid resin composition for a three-dimensional printer filament is characterized in that the heat deflection temperature (ASTM D648, 4.6 kgf/cm 2) is 100°C or higher, and the IZOD impact strength (ASTM D256, 23°C) is 4 kgfcm/cm or higher. Polylactic acid resin composition for 3D printer filament. Filament for a three-dimensional printer comprising the resin composition of any one of claims 1 to 8. The method of claim 11,
The filament is a filament for a three-dimensional printer, characterized in that the surface transition phenomenon of the resin does not occur when output under the following conditions.
[Output condition]
Using the filament, 35 g of output was output to a 3D printer set at a nozzle temperature of 200°C, an output speed of 110 mm/s, and a layer printing time of 10 seconds.