KR101715608B1 - Polylactic acid composition of filament for improving printing speed - Google Patents

Abstract

In a poly lactic acid composition for a three-dimensional printer filament, a three-dimensional printer filament which can increase the crystallization speed of a poly lactic acid resin by adding a nucleating agent and a resin of a specific composition to the poly lactic acid resin, A polylactic acid composition is disclosed. A polylactic acid composition for a three-dimensional printer filament, comprising (A) 97 to 99.9% by weight of a polylactic acid resin; And (B) 0.1 to 3% by weight of a coagulating agent; wherein the filament made of the poly (lactic acid) composition is used, and the surface migration phenomenon of the resin does not occur at the time of output under the following conditions. Lactic acid composition.
[Output condition]
Using the filament, 35 g of output is output to a three-dimensional printer set at a nozzle temperature of 200 ° C., an output speed of 110 mm / s, and a layer output time of 10 seconds.

Description

TECHNICAL FIELD [0001] The present invention relates to a polylactic acid composition for a three-dimensional printer filament,

The present invention relates to a polylactic acid composition for a three-dimensional printer filament, and more particularly to a polylactic acid composition for a three-dimensional printer filament for improving an output speed.

A three-dimensional (3-dimensional) printer is a device that produces three-dimensional objects by layering layers of fine thickness by sequentially injecting ink of a specific material. 3D printing is spreading in various fields. In addition to the automotive sector, which is composed of many parts, it is used by many manufacturers for making various models such as medical human body models, household products such as toothbrushes and razors.

Currently, the most widely used material for 3D printing is photopolymer, which is a photocurable macromolecule that solidifies upon receiving light. This accounts for 56% of the total market. The next most popular material is solid, thermoplastic, which is free to melt and solidify. It occupies 40% of the market and metal powder is expected to grow gradually in the future. The shape of the double thermoplastics material may be in the form of filaments, particles or powder powders. The three-dimensional printing of the filament type is faster than the other type in speed, so the productivity is high and the spreading speed is fast.

On the other hand, efforts to reduce greenhouse gases due to global warming have been extensively carried out. As one of the efforts, development of biodegradable polymer materials that are decomposed in nature has been attracting attention. Most of the existing polymers use petroleum resources as basic raw materials, but this may be exhausted in the future. Carbon dioxide generated by mass consumption of petroleum resources is recognized as a main cause of global warming. Therefore, attention has been focused on the development and industrial application of biodegradable polymers using plant resources grown by using carbon dioxide as a raw material. In particular, biodegradable polymer materials such as polylactic acid (PLA) have been actively applied as three-dimensional printer filaments.

However, poly (lactic acid) has a slow crystallization rate and has a limitation of slow 3D printing speed. The commercially available poly (lactic acid) filament weighs about 35 g and is about 70 × 61 × 64 mm in size.

Korean Prior Patent Publication No. 2012-0108798 discloses an L-type and D-type polylactic acid stereocomposite which is heated at a temperature of 100 to 110 ° C after cooling to cool the surface of a mold cavity. However, the application is limited to automobile materials and is not mentioned in the application of filaments for three-dimensional printers. The use of D-type polylactic acid causes a problem of cost burden .

Korean Patent Laid-Open Publication No. 2012-0129500 discloses a polylactic acid composition having improved mechanical properties and crystallization rate by applying phyllotaxis powder and carbon nanotubes subjected to organically surface-treated polylactic acid, and also as a nucleating agent for improving the crystallization speed However, the use of carbon nanotubes is not suitable as a material for a three-dimensional printer requiring various colors.

Korean Unexamined Patent Publication No. 2002-0022420 relates to a process for producing a heat-resistant poly (lactic acid) fiber blended with an L-type poly (lactic acid), a D-type poly (lactic acid) and a polyester, However, the application is limited to stretched fibers and is not mentioned in the application of filaments for three-dimensional printers. The use of D-type polylactic acid causes a problem of cost burden.

SUMMARY OF THE INVENTION Accordingly, the present invention has been made in order to solve the above problems, and it is an object of the present invention to provide a polylactic acid composition for a three-dimensional printer filament, which comprises a polylactic acid resin, A polylactic acid composition for a three-dimensional printer filament capable of improving the output speed of a printer, and a filament for a three-dimensional printer manufactured using the same.

In order to solve the above problems, the present invention provides a poly (lactic acid) composition for a three-dimensional printer filament, comprising (A) 97 to 99.9% by weight of a poly (lactic acid) resin; And (B) 0.1 to 3% by weight of a nucleating agent;

Wherein the filament made of the poly (lactic acid) composition is used so that the surface migration phenomenon of the resin does not occur during the output under the following conditions.

[Output condition]

Using the filament, 35 g of output is output to a three-dimensional printer set at a nozzle temperature of 200 ° C., an output speed of 110 mm / s, and a layer output time of 10 seconds.

Also, the polylactic acid resin (A) may be selected from the group consisting of poly-L-lactic acid (PLLA), poly-D-lactic acid (PDLA), stereo complex PLA and stereo block PLA The present invention provides a poly (lactic acid) composition for a three-dimensional printer filament, which comprises at least one selected from the group consisting of

The (B) nucleating agent is at least one selected from the group consisting of a talc type nucleating agent, a sodium phosphate salt type nucleating agent, an aromatic organic phosphate type nucleating agent, a sorbitol type nucleating agent and a calcium salt type nucleating agent. A polylactic acid composition for filament is provided.

And the sodium phosphate salt-based nucleating agent is methylenebis (4,6-di-tert-butylphenol) phosphate sodium salt. A polylactic acid composition for a printer filament is provided.

(C) 0.1 to 10 parts by weight of an amorphous resin or (D) 0.1 to 5 parts by weight of a polyolefin resin having at least one hydrophilic functional group, based on 100 parts by weight of the total of the polylactic acid resin (A) and the nucleating agent (B) The present invention further provides a polylactic acid composition for a three-dimensional printer filament.

The amorphous resin (C) may be at least one selected from the group consisting of polycarbonate, acrylonitrile butadiene styrene copolymer, polystyrene, styrene acrylonitrile copolymer, acrylonitrile styrene acrylate wherein the polyurethane resin is at least one selected from the group consisting of acrylonitrile styrene acrylate copolymer, polymethyl methacrylate, polysulfone, and polyethersulfone. Lt; / RTI >

In the polyolefin resin (D), the content of the hydrophilic functional group is 0.1 to 10% by weight.

The hydrophilic functional group may be at least one selected from the group consisting of acrylic, maleic anhydride, amine, carbonyl, hydroxyl and carboxyl. To provide a three-dimensional printer filament polylactic acid composition.

The polyolefin resin (D) is an ethylene vinyl acetate (EVA) resin having maleic anhydride as the hydrophilic functional group.

Also, the ethylene vinyl acetate (EVA) resin has a melt index (ASTM D 1238, 190 ° C, 2.16 kg) of 10 to 15 g / 10 min.

And a block copolymer or graft copolymer for forming a micro phase separation structure between the polylactic acid resin (A) and the amorphous resin (C), or between the polylactic acid resin (A) and the polyolefin resin (D) Is used in an amount of 0.5 to 10 parts by weight based on 100 parts by weight of the total of the polylactic acid resin (A) and the amorphous resin (C) or 100 parts by weight of the polylactic acid resin (A) and the polyolefin resin (D) The present invention further provides a polylactic acid composition for a three-dimensional printer filament,

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, The present invention provides a poly (lactic acid) composition for a three-dimensional printer filament, which is at least one selected from the group consisting of poly (caprolactone) polyester / poly (tetramethylene glycol) block polyol copolymer and methacrylate polystyrene copolymer.

The graft copolymer is at least one selected from the group consisting of a polypropylene-maleic anhydride graft copolymer, a polyethylene-maleic anhydride graft copolymer and a polyethylene-glycidyl methacrylate graft copolymer The present invention provides a polylactic acid composition for a three-dimensional printer filament.

The poly (lactic acid) composition for a three-dimensional printer filament according to the present invention is characterized by having a crystallization time of 300 seconds or less when the differential scanning calorimetry (110 ° C) is used.

In order to solve the above-mentioned problems, the present invention provides a filament for a three-dimensional printer made from the polylactic acid composition.

According to the present invention, by mixing the polylactic acid resin with a nucleating agent or a nucleating agent having a specific composition and an amorphous resin or polyolefin resin having a specific composition in an optimum amount to improve the crystallization speed, Providing printer output speed can have a big ripple effect on the 3D printer industry.

In addition, heat resistance and mechanical properties of a three-dimensional printer output produced using the polylactic acid composition according to the present invention can be improved.

1 shows a process of forming an L-shaped PLA and a D-shaped PLA structure and a stereocomplex PLA,
2 is a graph showing the results of measuring the crystallization time of the resin composition prepared according to Examples 1 to 5, Examples 15 to 21, and Comparative Example 1 using a differential scanning calorimeter,
Fig. 3 is a photograph showing the result of setting the conditions of the three-dimensional printer using the filament according to Comparative Example 2 at a temperature of 200 캜, an initial speed of 15 mm / s, an output speed of 40 mm / s, ,
Fig. 4 is a photograph showing the results of setting the conditions of the three-dimensional printer using the filament according to Comparative Example 2 at a temperature of 200 캜, an initial speed of 15 mm / s, an output speed of 110 mm / s, ,
Fig. 5 is a photograph showing the result of setting the conditions of the three-dimensional printer using the filament according to Comparative Example 2 at a temperature of 200 캜, an initial speed of 15 mm / s, an output speed of 110 mm / s, ,
Fig. 6 is a photograph showing the result of setting the conditions of a three-dimensional printer using a filament according to Comparative Example 2 at a temperature of 200 캜, an initial speed of 15 mm / s, an output speed of 110 mm / s, ,
7 is a graph showing the results of outputting the conditions of a three-dimensional printer set at a temperature of 200 캜, an initial speed of 15 mm / s, an output speed of 110 mm / s, and a time of outputting one layer of 10 seconds using the filament according to Example 22 ,
8 is a graph showing the results of setting the conditions of the three-dimensional printer using the filament according to Example 23 at a temperature of 200 캜, an initial speed of 15 mm / s, an output speed of 110 mm / s, ,
9 is a graph showing the results of setting the conditions of a three-dimensional printer using a filament according to Example 24 at a temperature of 200 캜, an initial speed of 15 mm / s, an output speed of 110 mm / s, ,
10 is a graph showing the results of setting the conditions of a three-dimensional printer using a filament according to Example 25 at a temperature of 200 캜, an initial speed of 15 mm / s, an output speed of 110 mm / s, .

Hereinafter, preferred embodiments of the present invention will be described in detail. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in detail with reference to the accompanying drawings. Throughout the specification, when an element is referred to as "including " an element, it means that it can include other elements, not excluding other elements, unless specifically stated otherwise.

As a result of intensive studies to solve the problem of crystallization speed of poly (lactic acid), which is a main cause of slow three-dimensional printer output speed, in a resin composition for a three-dimensional printer filament using a poly (lactic acid) resin, Nucleating agent or nucleating agent exhibits an improved crystallization rate and excellent mechanical properties when an amorphous resin or polyolefin resin having a specific composition is mixed at an optimum amount, leading to the present invention.

Accordingly, the present invention provides a polyphasic acid composition for a three-dimensional printer filament comprising (A) 97 to 99.9% by weight of a polylactic acid resin and (B) 0.1 to 3% by weight of a nucleating agent, wherein the filament made of the above- Disclosed is a poly (lactic acid) composition for a three-dimensional printer filament that does not cause a surface migration phenomenon of a resin when outputting 35 g of a product with a three-dimensional printer set at a temperature of 200 캜, an output speed of 110 mm / s, and a layer output time of 10 seconds.

In the present invention, the term "resin surface migration phenomenon" refers to a phenomenon in which a resin component is discharged from a final output surface to a surface of a printed product at a high output speed when a filament is made of a poly It is the phenomenon that it becomes not smooth.

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

The polylactic acid (hereinafter abbreviated as "PLA") may be composed of repeating units derived from L-isomeric lactic acid, repeating units derived from D-isomeric lactic acid, or repeating units derived from L, D-isomeric lactic acid PLA can be formed by polymerizing (stereo complex PLA or stereo block PLA) the repeat units derived from L-isomer and D-isomeric lactate either alone (PLLA or PDLA) or in combination. 1 shows the process of forming a stereocomplex PLA together with an L-type PLA and a D-type PLA structure. In Table 1, a glass of a single-component L-type PLA (PLLA) and a stereo complex PLA formed at a 50:50 weight% The transition temperature (Tg), melting temperature (Tm), crystalline structure and melting enthalpy change were compared.

In the present invention, when PLA is used as the biodegradable polyester resin, PLLA, PDLA, stereocomplex PLA and stereoblock PLA may be used alone or in combination.

When PLLA is used, the repeating units derived from L-isomeric lactic acid are preferably 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, it is more preferable that 95 to 100% by weight of the repeating unit derived from the L-isomeric lactic acid and 0 to 5% by weight of the repeating unit derived from the D-isomeric lactic acid are considered.

The PLLA is not particularly limited in terms of molecular weight and molecular weight distribution if it can be processed, but it is preferable to use a PLLA having a weight average molecular weight of 80,000 or more from the viewpoint of balance of mechanical strength and heat resistance of a molded article, and a weight average molecular weight of 90,000 to 500,000 Is more preferable.

When PDLA is used, the repeating units derived from D-isomeric lactic acid are preferably 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, it is more preferable that 95 to 100% by weight of the repeating unit derived from the D-isomeric lactic acid and 0 to 5% by weight of the repeating unit derived from the L-isomeric lactic acid are taken into account in consideration of the hydrolysis resistance.

There is no particular limitation on the molecular weight or the molecular weight distribution of the PDLA. However, it is preferable to use a PDLA having a weight average molecular weight of 10,000 or more for increasing the crystallization rate, more preferably 20,000 to 100,000.

In the present invention, the polylactic acid preferably has a melt index of 2 to 15 g / 10 min (210 ° C, 2.16 kg), more preferably 3 to 10 g / 10 min, most preferably 5 to 10 g / 10 min. If the PLA has a melt index of less than 2 g / 10 min or more than 15 g / 10 min, impact strength and processability may be deteriorated.

The crude nucleating agent used in the present invention is an additive which improves processing productivity by effectively reducing the crystal size of the poly (lactic acid) resin and improving the three-dimensional printer output speed by decreasing the crystallization time as the crystallization degree is increased. D-type polylactic acid can also serve as a nucleating agent, but the effect as a nucleating agent is lower than the nucleating agent used in the present invention depending on the high resin cost and the content.

The crude nucleating agent is contained in an amount of 0.1 to 3% by weight, preferably 0.1 to 1% by weight, more preferably 0.1 to 0.5% by weight in order to exhibit an appropriate crystallization rate. If the content of the nucleating agent is less than 0.1% by weight, the performance of the nucleating agent may be difficult to exhibit. If the content of the nucleating agent exceeds 3% by weight, the degree of crystallization of the resin increases and the rigidity increases. The physical properties of the resin may not be balanced.

As the nucleating agent, a talc type nucleating agent, a sodium phosphate salt type nucleating agent, an aromatic organic phosphate type nucleating agent, a sorbitol type nucleating agent or a calcium salt type nucleating agent may be preferably used. Although the sodium phosphate salt-based nucleating agent is not particularly limited, methylenebis (4,6-di-tert-butylphenol) phosphate sodium salt is preferable. Lt; / RTI >

In the present invention, by mixing the amorphous resin with the polylactic acid resin and the nucleating agent, it is possible to improve the mechanical properties such as the impact strength while improving the crystallization speed in the final resin composition to be produced.

The amorphous resin is not particularly limited and includes, for example, polycarbonate, acrylonitrile butadiene styrene copolymer, polystyrene, styrene acrylonitrile copolymer, acrylonitrile Acrylonitrile styrene acrylate copolymer, polymethyl methacrylate, polysulfone, polyethersulfone, etc. may be used alone or in combination. Preferably, polycarbonate Resins can be used. When a polycarbonate resin is used, the melt index (ASTM D1238, 300 ° C, 1.2 kg) of 1 to 20 g / 10 min, preferably 5 to 15 g / 10 min is very advantageous in improving the crystallization speed and mechanical properties .

The amorphous resin may be added in an amount of 0.1 to 10 parts by weight, preferably 1 to 10 parts by weight, more preferably 1 to 5 parts by weight, based on 100 parts by weight of the total of the polylactic acid resin (A) and the nucleating agent (B) And the like. If the content of the amorphous resin is less than 0.1 part by weight, the content of the amorphous resin may be small and it may be difficult to improve the crystallization speed. If the amount of the amorphous resin is more than 10 parts by weight,

In the present invention, the polyolefin resin having at least one hydrophilic functional group is mixed with the polylactic acid resin and the nucleating agent to thereby exhibit an improvement in the crystallization speed of the resin composition, while having a proper amount of hydrophilic functional groups in the polyolefin resin, The surface transition phenomenon of the resin can be minimized without lowering the crystallization rate in the final resin composition.

The polyolefin resin preferably has a hydrophilic functional group content of 0.1 to 10% by weight, more preferably 0.2 to 3% by weight. If the content of the hydrophilic functional group is less than 0.1% by weight, it may be difficult to obtain the effect of inhibiting the surface migration phenomenon of the resin. If the content of the hydrophilic functional group is more than 10% by weight, The physical properties may be lowered.

Examples of such hydrophilic functional groups include acrylic, maleic anhydride, amine, carbonyl, hydroxyl, carboxyl, and the like, and in particular, maleic anhydride It is preferable to prevent the surface migration phenomenon at the time of output using the final resin composition.

As the base resin of the polyolefin resin having hydrophilic functional group, it is not particularly limited and examples thereof include polyethylene, polypropylene, polybutene, polyisobutylene, polymethylpentene, ethylene and propylene copolymer, ethylene and butene copolymer, A copolymer, an ethylene vinyl acetate (EVA) resin, or the like may be used alone or in combination. Ethylene vinyl acetate resin may be preferably used. When the ethylene vinyl acetate resin is used, the melt index (ASTM D1238, 190 ° C, 2.16 kg) of 10 to 15 g / 10 min is very advantageous for improving the impact strength of the resin as well as preventing surface migration of the resin, It has been confirmed that when the maleic acid is contained in the above-mentioned preferable amount, the ability of the resin composition of the final resin composition to prevent the surface migration phenomenon of the resin can be maximized.

In the present invention, the polyolefin resin having at least one hydrophilic functional group may be contained in an amount of 0.1 to 5 parts by weight, preferably 1 to 3 parts by weight, based on 100 parts by weight of the total of (A) the polylactic acid resin and (B) . When the content of the polyolefin resin is less than 0.1 part by weight, it may be difficult to expect an improvement in the crystallization speed and an effect of preventing surface migration of the resin, and if the content is more than 5 parts by weight, the degree of crystallization rate improvement may be lowered in a supersaturated state.

In the present invention, for good mixing of the polylactic acid resin (A) and the amorphous resin (C), or for the good mixing of the polyolefin resin (A) and the polyolefin resin having at least one hydrophilic functional group (D) I can include more.

The compatibilizing agent is a material capable of forming and stabilizing a micro phase separation structure by alleviating the difference in properties between a biodegradable resin having a crystal and a non-crystalline resin, and improving the mechanical properties such as impact strength while maintaining an improved crystallization rate of the final resin composition For example. To this end, the content of the compatibilizer is preferably 0.5 to 10 parts by weight per 100 parts by weight of the total of the polylactic acid resin (A) and the amorphous resin (C) or 100 parts by weight of the polylactic acid resin (A) , And preferably 1 to 5 parts by weight. If the content of the compatibilizer is less than 0.5 parts by weight, compatibility with the resin may be weakened, and mechanical properties such as impact strength may be deteriorated. If the content exceeds 10 parts by weight, the compatibilizer may not be effective in improving the physical properties.

The compatibilizing agent is not particularly limited as long as it can achieve good mixing of (A) a poly (lactic acid) resin, (C) an amorphous resin or (A) a poly (lactic acid) resin and (D) a polyolefin resin having at least one hydrophilic functional group , For example, a block copolymer compatibilizer or a graft copolymer compatibilizer may be used, and a graft copolymer compatibilizer may be preferably used.

Examples of the block copolymer compatibilizer include styrene-ethylene / butylene / styrene (SEBS) block copolymer, styrene-ethylene / propylene-styrene (SEPS) block copolymer, methacrylic block copolymer, polycaprolactone polyester Ethylene / butylene / styrene (SEBS) block copolymer, styrene (ethylene / butylene / styrene) block copolymers, -Ethylene / propylene-styrene (SEPS) block copolymer may be used.

Examples of the graft copolymer compatibilizer include a polypropylene-maleic anhydride graft copolymer, a polyethylene-maleic anhydride graft copolymer, and a polyethylene-glycidyl methacrylate graft copolymer. Maleic anhydride graft copolymer alone or in a polypropylene-maleic anhydride graft copolymer with a polyethylene-maleic anhydride graft copolymer or a polyethylene-glycidyl methacrylate graft copolymer It can be used in mixed form.

The polylactic acid resin composition for use in the production of the filament for a three-dimensional printer according to the present invention may further contain other additives in addition to the above-mentioned main components within the scope of the intended use or effect. For example, heat stabilizers, light stabilizers, flame retardants, carbon black, antioxidants, impact modifiers, and the like may be further added to the composition, and other additives may be added in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the final resin composition excluding additives Lt; / RTI >

The filament for a three-dimensional printer according to the present invention has improved crystallization speed, and is capable of outputting a three-dimensional printer at an extremely high speed, as well as improving heat resistance and improving mechanical properties in mixing amorphous resin. That is, it is possible to provide a filament for a three-dimensional printer having a crystallization time of not more than 300 seconds when evaluated by differential scanning calorimetry (110 ° C).

Also, it is possible to provide a filament for a three-dimensional printer capable of performing precise output without any surface transition phenomenon of a resin even at a speed of 110 mm / s or more for a three-dimensional printer output and a maximum output time of 10 seconds for a single- do.

The poly (lactic acid) resin composition used for producing the filament for a three-dimensional printer according to the present invention can be produced by a known melt extrusion method for producing a general resin composition. That is, a polylactic acid resin, a nucleating agent, an amorphous resin, a compatibilizer, and other additives may be mixed at the same time and then melt-extruded in an extruder to produce a desired product.

For example, the components are first mixed in an appropriate amount. At this time, mixing may be performed by arbitrarily selecting mixing means which are 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 DEG C by using a twin-screw extruder and molded into a pellet state. Thereafter, the resin composition molded into pellets is extruded by a single-screw extruder at 170 to 200 ° C, cooled, and wound up to be re-formed into filaments having a constant diameter, and can be used for a three-dimensional printer filament. The filament may be extruded by a single screw extruder having a screw diameter of 20 to 40 mm and a screw length of 100 to 110 mm, cooling the filament using a cooling water bath, and winding the filament into a filament having a diameter of 1.5 to 2 mm.

Hereinafter, a specific embodiment of 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

A PLA product Ingeo 4032D (melt index 7 g / 10 min (210 캜, 2.16 kg) manufactured by NatureWorks LLC, USA) was used.

(2) nucleating agent

Nuclear agent product NA-902 manufactured by ADEKA of Japan, HPN-20E, HPN-68L and HPN-600e manufactured by Milliken USA, manufactured by Nissan of Japan, Ecopromote TF, Nuclear product KC2000 manufactured by KOCH Were used.

(3) Amorphous resin

Amorphous resin PC-1100 (melt index: 10 g / 10 min (300 ° C, 1.2 kg)) manufactured by Lotte Chemical Co., Ltd. was used.

(4) a polyolefin resin having at least one hydrophilic functional group

(Modified Polyolefin) product Adpoly EV-600 (melt index 10 to 15 g / 10 min (190 캜, 2.16 kg)) manufactured by Lotte Chemical Co., Ltd. was used. EV-600 is an MPO product with hydrophilic functional groups of maleic anhydride in ethylene vinyl acetate (EVA) series.

(5) compatibilizer

A polypropylene-maleic anhydride graft copolymer (PH-200, maleic anhydride graft ratio: 3.9%) produced by Lotte Chemical Co., Ltd. was used as a graft copolymer.

(6) Phenolic antioxidants

To prevent thermal decomposition of the resin composition, Irganox (R) 010 manufactured by Ciba Inc. was used.

Example  One

99.7 parts by weight of a polylactic acid resin, 0.3 parts by weight of a nucleating agent Ecopromote TF, and 0.1 phr of a phenol-based antioxidant (0.1 parts by weight based on 100 parts by weight of the total components excluding the additives) were mixed for 5 minutes using a tumbler mixer, , Extruded in a biaxial extruder having a diameter of 40 mm at a temperature range of 170 to 200 ° C, and then extruded into a pellet form. The extruded pellets were dried at 80 DEG C for 12 hours.

Example  2

Pellets were 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. [

Example  3

Pellets were prepared in the same manner as in Example 1, except that 0.3 parts by weight of the coagulating agent NA-902 was mixed in Example 1. [

Example  4

Pellets were prepared in the same manner as in Example 1, except that 0.3 parts by weight of the coagulating agent HPN-20E was used.

Example  5

Pellets were prepared in the same manner as in Example 1 except that 0.3 parts by weight of the nucleating agent HPN-600ei was used in Example 1. [

Example  6

Pellets were prepared in the same manner as in Example 1, except that 0.1 parts by weight of the nucleating agent Ecopromote TF was mixed in Example 1. [ After extruded pellets were dried at 80 ° C for 12 hours, ASTM specimens were injection-molded (after cooling at an injection temperature of 180 to 200 ° C for 80 seconds) using an injection machine with a mold-clamping force of 150 tons (Dongshin Hydraulic Co., Respectively.

Example  7

A physical property specimen was prepared in the same manner as in Example 6, except that 0.3 parts by weight of a nucleating agent Ecopromote TF was mixed in Example 6. [

Example  8

A physical property specimen was prepared in the same manner as in Example 6, except that 0.5 parts by weight of a nucleating agent Ecopromote TF was mixed in Example 6. [

Example  9

A physical property specimen was prepared in the same manner as in Example 6, except that 0.1 part by weight of a nucleating agent KC2000 was mixed in Example 6. [

Example  10

A physical property specimen was prepared in the same manner as in Example 6, except that 0.3 parts by weight of a nucleating agent KC2000 was mixed in Example 6. [

Example  11

A physical property specimen was prepared in the same manner as in Example 6, except that 0.5 parts by weight of a nucleating agent KC2000 was mixed in Example 6. [

Example  12

A physical property specimen was prepared in the same manner as in Example 6, except that 0.1 parts by weight of the coagulating agent NA-902 was mixed in Example 6.

Example  13

A physical property specimen was prepared in the same manner as in Example 6, except that 0.3 parts by weight of the coagulating agent NA-902 was used in Example 6.

Example  14

A physical property specimen was prepared in the same manner as in Example 6, except that 0.5 parts by weight of the coagulating agent NA-902 was used in Example 6.

Example  15

A physical property specimen was prepared in the same manner as in Example 6 except that 1 part by weight of the amorphous resin and 3 parts by weight of the compatibilizer were further mixed in Example 6.

Example  16

A physical property specimen was prepared in the same manner as in Example 6, except that 3 parts by weight of the amorphous resin and 3 parts by weight of the compatibilizer were further mixed in Example 6.

Example  17

A physical property specimen was prepared in the same manner as in Example 6, except that 5 parts by weight of the amorphous resin and 3 parts by weight of the compatibilizer were further mixed in Example 6.

Example  18

A physical property specimen was prepared in the same manner as in Example 6, except that 10 parts by weight of the amorphous resin and 3 parts by weight of the compatibilizer were further mixed in Example 6.

Example  19

A physical property specimen was prepared in the same manner as in Example 6, except that 1 part by weight of a polyolefin resin having at least one hydrophilic functional group in Example 6 and 3 parts by weight of a compatibilizing agent were further mixed.

Example  20

A physical property specimen was prepared in the same manner as in Example 6 except that 3 parts by weight of a polyolefin resin having at least one hydrophilic functional group in Example 6 and 3 parts by weight of a compatibilizing agent were further mixed.

Example  21

5 parts by weight of a polyolefin resin having at least one hydrophilic functional group in Example 6 and 3 parts by weight of a compatibilizing agent were further mixed to prepare a physical property specimen in the same manner as in Example 6. [

Example  22

The pellets produced in Example 1 were extruded by a single-screw extruder at 170 to 200 DEG C, and then cooled and taken up to produce filaments having a constant diameter of 1.75 mm.

Example  23

The pellets prepared in Example 2 were extruded by a single-screw extruder at 170 to 200 DEG C, and then cooled and taken up to produce filaments having a constant diameter of 1.75 mm.

Example  24

The pellets prepared in Example 16 were extruded by a single-screw extruder at 170 to 200 DEG C, followed by cooling and winding to prepare filaments having a constant diameter of 1.75 mm.

Example  25

The pellets prepared in Example 20 were extruded by a single screw extruder at 170 to 200 DEG C, and then cooled and taken up to produce filaments having a constant diameter of 1.75 mm.

Comparative Example  One

Pellets were prepared in the same manner as in Example 1 except that 100 parts by weight of the polylactic acid resin was used without mixing the nucleating agent, the amorphous resin or the polyolefin resin having at least one hydrophilic functional group in Example 1. The extruded pellets were dried at 80 ° C for 12 hours, and then ASTM specimens were injection molded using an injection machine (Dongshin Hydraulic Co., Ltd., Korea) having a mold clamping force of 150 tons. Further, the extruded pellets were extruded by a single-screw extruder at 170 to 200 DEG C, followed by cooling and winding to obtain filaments having a constant diameter of 1.75 mm.

Comparative Example  2

Polyunsaturated filament MW10 (Natural) manufactured by Canon Korea was used.

The composition (unit: parts by weight) of the resin composition prepared according to the above Examples and Comparative Examples is shown in Table 2 below.

Test Example 1

In order to evaluate the crystallization speed enhancement of the resin composition for a three-dimensional printer filament according to the present invention, the resin compositions prepared according to Examples 1 to 5, Examples 15 to 21, and Comparative Example 1 were subjected to differential scanning calorimetry (DSC (DSC Q200, TA Instrument). The temperature of each specimen was increased from 30 ° C. to 250 ° C. at a rate of 20 ° C./minute and then quenched at a rate of 80 ° C./minute, and the crystallization time measured at 110 ° C. Is shown in Fig.

Referring to FIG. 2, when the nucleating agent and the additive resin are mixed in the poly (lactic acid) resin according to the present invention, the crystallization speed of the poly (lactic acid) resin is improved by about 50% or more.

Test Example 2

The heat distortion temperature, impact strength and tensile strength of the specimens prepared according to Examples 6 to 21 and Comparative Example 1 were evaluated in order to evaluate the physical properties of the resin composition for a three-dimensional printer filament according to the present invention, Respectively. The specimens prepared according to Examples 6 to 14 and Comparative Example 1 were subjected to annealing at a temperature of 100 ° C for 1 hour and then evaluated according to ASTM standards. The specimens prepared according to Examples 15 to 21 and Comparative Example 1 The specimens were evaluated according to the ASTM standard without annealing in order to evaluate the effect of amorphous resin or polyolefin resin having at least one hydrophilic functional group.

Referring to Table 3, in the case of the specimens (Examples 6 to 14) prepared by mixing the optimum amounts of the polylactic acid resin and the specific nucleating agent according to the present invention, the specimen prepared with 100 parts by weight of the polylactic acid resin (Comparative Example 1 after annealing) , The heat distortion temperature was 129%, the impact strength was 124%, and the tensile strength was 101%.

In addition, in the case of specimens (Examples 15 to 18) prepared by mixing an optimum amount of a specific amorphous resin with a polylactic acid resin and a nucleating agent, the heat distortion temperature was 102% higher than that of the specimen prepared with 100 parts by weight of the polylactic acid resin (Comparative Example 1) , Impact strength of 142% and tensile strength of 109%.

In addition, in the case of the specimens (Examples 19 to 21) prepared by mixing the polyolefin resin having at least one hydrophilic functional group in the polylactic acid resin and the nucleating agent with the optimum content, compared with the specimen prepared with 100 parts by weight of polylactic acid (Comparative Example 1) The impact strength was improved to 224%, and the breakdown point elongation and HDT deterioration did not occur. However, since the tensile strength is lowered, it can be seen that the mixing ratio of the resin having at least one hydrophilic functional group is limited.

Test Example 3

In order to evaluate the three-dimensional printer output performance of the filament made of the resin composition according to the present invention, the output performance of each filament manufactured according to Examples 22 to 25 and Comparative Example 2 was evaluated using a three-dimensional printer. The three-dimensional printer was a MARV manufactured by Canon Korea.

In order to compare the output performance, the conditions of the three-dimensional printer using the existing filament according to Comparative Example 2 were adjusted to 200 ° C, initial speed 15 mm / s, output speed 40 mm / s, (Fig. 4), 110 mm / s and 20 seconds (Fig. 5), 110 mm / s (Fig. And 10 seconds (Fig. 6). The results are shown in Figs. 3 to 6.

Using the filaments prepared according to Examples 22 to 25, the condition of the three-dimensional printer was adjusted to 200 ° C, initial speed 15 mm / s, output speed 110 mm / s, and the time for outputting one layer to 10 seconds, (Output weight), and the results are shown in Figs. 7 to 10, respectively.

As a result of the output, it was found that when the output was 40 mm / s using a conventional filament (Comparative Example 2) and the output time of one layer was 30 seconds, the surface migration phenomenon of the resin did not appear, It is confirmed that the output efficiency is not good. When the output condition is severe (refer to Figs. 4 to 6), it can be seen that the state of the surface of the output material is deteriorated due to the surface migration phenomenon of the resin.

However, according to the present invention, when filaments prepared by mixing a nucleating agent or a nucleating agent having a specific composition with a specific composition additive resin according to the present invention are used, the output speed is 110 mm / s and the output time of one layer is 10 seconds. (Output time of about 2 hours), the output time was shortened about 5 times, but it can be confirmed that the output performance is kept good without surface migration of the resin.

The preferred embodiments of the present invention have been described in detail above. It will be understood by those of ordinary skill in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.

Accordingly, the scope of the present invention is defined by the appended claims rather than the foregoing detailed description, and all changes or modifications derived from the meaning, range, and equivalence of the claims are included in the scope of the present invention Should be interpreted.

Claims (15)

A polylactic acid composition for a three-dimensional printer filament,
(A) 97 to 99.9% by weight of polylactic acid resin;
(B) 0.1 to 3% by weight of a nucleating agent; And
(D) 0.1 to 5 parts by weight of a polyolefin resin having at least one hydrophilic functional group, based on 100 parts by weight of the total of the polylactic acid resin (A) and the nucleating agent (B);
, ≪ / RTI &
Wherein the polyolefin resin (D) is an ethylene vinyl acetate (EVA) resin having maleic anhydride as the hydrophilic functional group. The method according to claim 1,
The polylactic acid resin (A) is selected from the group consisting of poly-L-lactic acid (PLLA), poly-D-lactic acid (PDLA), stereo complex PLA and stereo block PLA Wherein the polylactic acid composition is a polylactic acid composition. The method according to claim 1,
Wherein the (B) nucleating agent is at least one selected from the group consisting of a talc type nucleating agent, a sodium phosphate salt type nucleating agent, an aromatic organic phosphate type nucleating agent, a sorbitol type nucleating agent and a calcium salt type nucleating agent. ≪ / RTI > The method of claim 3,
Wherein the sodium phosphate salt-based nucleating agent is methylenebis (4,6-di-tert-butylphenol) phosphate sodium salt. Polylactic acid composition for filament. The method according to claim 1,
(C) 0.1 to 10 parts by weight of an amorphous resin, based on 100 parts by weight of the total of (A) the polylactic acid resin and (B) the nucleating agent. 6. The method of claim 5,
The amorphous resin (C) may be at least one selected from the group consisting of polycarbonate, acrylonitrile butadiene styrene copolymer, polystyrene, styrene acrylonitrile copolymer, acrylonitrile styrene acrylate wherein the polyurethane resin composition is at least one selected from the group consisting of acrylonitrile styrene acrylate copolymer, polymethyl methacrylate, polysulfone, and polyethersulfone. . The method according to claim 1,
The polyolefin resin (D) has a hydrophilic functional group content of 0.1 to 10% by weight. delete delete The method according to claim 1,
Wherein the ethylene vinyl acetate (EVA) resin has a melt index (ASTM D 1238, 190 캜, 2.16 kg) of 10 to 15 g / 10 min. 6. The method of claim 5,
A block copolymer or graft copolymer for forming a micro phase separation structure between the polylactic acid resin (A) and the amorphous resin (C), or between the polylactic acid resin (A) and the polyolefin resin (D) (C) 100 parts by weight of the total of the polylactic acid resin (A) and the amorphous resin (A) or the polyolefin resin (A) and 100 parts by weight of the total amount of the polyolefin resin (D) Wherein the polylactic acid composition for a three-dimensional printer filament is a polylactic acid composition for a three-dimensional printer filament. 12. The method of claim 11,
The block copolymers may be selected from the group consisting of styrene-ethylene / butylene / styrene (SEBS) block copolymers, styrene-ethylene / propylene-styrene (SEPS) block copolymers, methacrylic block copolymers, polycaprolactone polyester copolymers, Wherein the at least one polymer is at least one selected from the group consisting of caprolactone polyester / poly (tetramethylene glycol) block polyol copolymer and methacrylate polystyrene copolymer. 12. The method of claim 11,
The graft copolymer is at least one selected from the group consisting of a polypropylene-maleic anhydride graft copolymer, a polyethylene-maleic anhydride graft copolymer, and a polyethylene-glycidyl methacrylate graft copolymer By weight based on the total weight of the three-dimensional printer filament. The method according to claim 1,
Wherein the polylactic acid composition has a crystallization time of 300 seconds or less when evaluated by differential scanning calorimetry (110 ° C). 14. A filament for a three-dimensional printer made from the polylactic acid composition according to any one of claims 1 to 7 and 10 to 14.

Images