KR101685760B1 - Biodegradable resin composition having improved paint-abillity and impact streangth for three dimensional printer filament - Google Patents

Abstract

In a resin composition for a three-dimensional printer filament using a biodegradable resin such as polylactic acid, a resin composition for a three-dimensional printer filament using a biodegradable resin which can solve the drawability problem due to the adoption of a biodegradable resin, / RTI > (A) 50 to 95% by weight of a biodegradable resin; And (B) 5 to 50% by weight of a polyolefin resin having at least one hydrophilic functional group.

Description

FIELD OF THE INVENTION [0001] The present invention relates to a biodegradable resin composition for a three-dimensional printer filament having improved colorability and impact strength,

The present invention relates to a biodegradable resin composition for a three-dimensional printer filament, and more particularly to a biodegradable resin composition for a three-dimensional printer filament having improved colorability and impact strength.

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.

2. Description of the Related Art Biodegradable polymer materials such as polylactic acid (PLA) have been actively used as a three-dimensional printer filament material. However, most of the three-dimensional printer injection molds have monochromatic colors. Therefore, users often perform additional coloring operations. However, currently used resins are inferior in colorability due to their characteristics.

Korean Patent Registration No. 0838878 refers to a polymer containing methacrylate as a monomer as a composition for a three-dimensional printer, but relates to a thermosetting composition. It relates to the use of a biodegradable resin and improvement of colorability of an injection molded article .

Korean Patent No. 1350993 discloses a thermoplastic filament resin composition for a three-dimensional printer, which is based on a biodegradable resin, but does not mention component mixing for improving colorability of an injection molded article.

Korean Patent No. 1394119 relates to a thermoplastic filament resin composition for a three-dimensional printer, and although the use of a biodegradable resin is mentioned in the background art, no reference is made to mixing of components for improving colorability of an injection molded article.

SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a resin composition for a three-dimensional printer filament using a biodegradable resin such as polylactic acid, which is capable of securing high impact strength while solving color- The present invention provides a resin composition for a three-dimensional printer filament using the biodegradable resin.

In order to solve the above-mentioned problems, the present invention provides a thermoplastic resin composition comprising (A) 50 to 95% by weight of a biodegradable resin; And (B) 5 to 50% by weight of a polyolefin resin having at least one hydrophilic functional group.

Also, the biodegradable resin is a biodegradable polyester resin produced by condensation polymerization of an aliphatic dicarboxylic acid, an aromatic dicarboxylic acid, or a mixture thereof and a diol compound, and provides a biodegradable resin composition for a three-dimensional printer filament .

The biodegradable polyester resin may be selected from the group consisting of polylactic acid (PLA), polybutylene succinate (PBS), polybutylene adipate-co-terephthalate (PBAT), poly (butylene adipate-co-butylene terephthalate) And at least one selected from the group consisting of PBGT (polybutylene glutarate-co-terephthalate) and PHB (polyhydroxybutyrate).

Also, the polyolefin resin has a hydrophilic functional group content of 0.1 to 10% by weight, and the biodegradable resin composition for a three-dimensional printer filament is provided.

Wherein said hydrophilic functional group is selected from the group consisting of acrylic, maleic anhydride, amine, carbonyl, hydroxyl and carboxyl. Disclosed is a biodegradable resin composition for a 3D printer filament.

And the polyolefin resin is an ethylene vinyl acetate (EVA) resin having maleic anhydride as the hydrophilic functional group. The present invention also provides a biodegradable resin composition for a three-dimensional printer filament.

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.

A compatibilizing agent containing a block copolymer or a graft copolymer for forming a micro phase separation structure between the biodegradable resin and the polyolefin resin is added in an amount of 0.5 to 10 wt% based on 100 parts by weight of the total of the biodegradable resin and the polyolefin resin The present invention provides a biodegradable resin 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 biodegradable resin composition for a three-dimensional printer filament, wherein the biodegradable resin composition is at least one selected from the group consisting of polycaprolactone 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 biodegradable resin composition for a three-dimensional printer filament.

The composition according to the following evaluation method (ASTM F 1842) has a paintability grade of 5 in the acrylic paint, 4 in the enamel paint and 5 in the lacquer paint. To provide a resin composition.

[Evaluation method of paintability]

Using this composition, a 3 mm thick paint sample was prepared with a press molding machine. The paint was painted on the specimen, dried and cut into 25 grid patterns using a cutting tool on the painted area, Tape, 3M) was evenly applied to the painted area and peeled off at an angle of 180 ° to evaluate the degree of peeling of the paint.

Also, the composition has an IZOD impact strength (ASTM D 256) of 8 kgf / cm or more, and provides a biodegradable resin composition for a three-dimensional printer filament.

According to the present invention, it is possible to provide a biodegradable resin composition for a three-dimensional printer filament that contains a polyolefin resin having at least one hydrophilic functional group in an appropriate amount to improve colorability of an injection molded article and have high impact strength.

In addition, the present invention provides a three-dimensional printer injection molding exhibiting excellent colorability and impact strength-related physical properties as compared with the conventional biodegradable resin composition, thereby providing a large ripple effect to the three-dimensional printer industry.

1 shows a process of forming an L-shaped PLA and a D-shaped PLA structure and a stereocomplex PLA,
Fig. 2 is a photograph showing a comparison of the results of the paintability evaluation of the acrylic paint of the specimen made of the resin composition prepared according to the examples and the comparative example,
Fig. 3 is a photograph showing comparison of paintability evaluation results of an enamel paint of a specimen made of a resin composition produced according to Examples and Comparative Examples,
FIG. 4 is a photograph showing a comparison of results of colorability evaluation of a specimen made of a resin composition prepared according to Examples and Comparative Examples with respect to a lacquer-based paint.

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.

DISCLOSURE OF THE INVENTION The present inventors have made intensive studies to solve the problem of poor colorability of a resin composition for a three-dimensional printer filament using a biodegradable resin such as polylactic acid, The polyolefin resin having a hydrophilic functional group in the resin is mixed with an appropriate amount, and the resulting polyolefin resin exhibits an additional improved impact strength along with an improved coloring property.

Accordingly, the present invention relates to (A) 50 to 95% by weight of a biodegradable resin; And (B) 5 to 50% by weight of a polyolefin resin having at least one hydrophilic functional group. The present invention also provides a biodegradable resin composition for a three-dimensional printer filament.

In the present invention, the (A) biodegradable resin is not particularly limited as long as it is a resin capable of improving colorability by mixing with a polyolefin resin having at least one hydrophilic functional group described later, An aromatic dicarboxylic acid or a mixture thereof and a diol compound. Examples of such biodegradable polyester resins include polylactic acid (PLA), polybutylene succinate (PBS), polybutylenedi adipate-co-terephthalate (PBAT), poly (butylene adipate-co-butylene succinate-co-butylene terephthalate ), Polybutylene glutarate-co-terephthalate (PBGT), and polyhydroxybutyrate (PHB). These resins may be used singly or in combination of two or more, preferably PLA.

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

The PLA may be composed of a repeating unit derived from an L-isomeric lactate, a repeating unit derived from a D-isomeric lactate, or a repeating unit derived from an L, D-isomeric lactate, wherein the PLA is an L-isomer and a D- (Stereocomplex PLA or stereo block PLA) of the repeating units derived from lactic acid 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 (T _g ), melting temperature (T _m ), 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.

When PLA is used as the biodegradable polyester resin in the present invention, the PLA 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, / 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.

In the present invention, the biodegradable resin is contained in an amount of 50 to 95% by weight, preferably 70 to 90% by weight. If the content of the biodegradable resin is less than 50% by weight, the flexibility of the final resin composition may be deteriorated. If the content of the biodegradable resin is more than 95% by weight, the impact strength may be decreased and the effect of improving the colorability may not be expected .

In the present invention, the polyolefin resin (B) having at least one hydrophilic functional group (B) has a hydrophilic functional group in a proper amount in the polyolefin resin, so that the final resin composition prepared by mixing with the biodegradable resin So that it is possible to exhibit excellent coloring property.

At this time, in order to improve the colorability of the final resin composition, the polyolefin resin preferably has a hydrophilic functional group content of 0.1 to 10 wt%, more preferably 0.2 to 3 wt%. If the content of the hydrophilic functional group is less than 0.1% by weight, it may be difficult to obtain an improvement in colorability. If the content of the hydrophilic functional group is more than 10% by weight, compatibility with the hydrophilic action period may be reduced due to increased agglomeration, have.

Examples of the hydrophilic functional group for improving the coloring property include acrylic, maleic anhydride, amine, carbonyl, hydroxyl, carboxyl, and the like. In particular, when maleic anhydride is used, it is preferable to improve the colorability of 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 D 1238, 190 ° C, 2.16 kg) of 10 to 15 g / 10 min is very advantageous for improving the impact strength as well as improving the coloring property. Further, as the hydrophilic functional group, Is contained in the above-mentioned preferable amount, it is confirmed that the degree of enhancement of the colorability of the final resin composition can be maximized.

In the present invention, the polyolefin resin having at least one hydrophilic functional group is contained in an amount of 5 to 50% by weight, and preferably 10 to 30% by weight. If the content of the polyolefin resin is less than 5% by weight, the impact strength may be lowered and the effect of improving the colorability may not be expected. If the content is more than 50% by weight, the flexibility of the final resin composition may be deteriorated.

The present invention may further comprise a compatibilizer for good mixing of the biodegradable resin (A) and the polyolefin resin (B) having at least one hydrophilic functional group. The compatibilizing agent is a substance having the ability to form and stabilize a micro phase separation structure by alleviating the difference in properties between the biodegradable resin and the resin having at least one hydrophilic functional group, thereby improving the impact strength while maintaining the improved colorability of the final resin composition. Can be included in the optimal amount for the purpose. For this purpose, the content of the compatibilizer may be 0.5 to 10 parts by weight, preferably 1 to 5 parts by weight, based on 100 parts by weight of the total of the biodegradable resin (A) and the polyolefin resin (B). 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 (A) a biodegradable resin and (B) a polyolefin resin having at least one hydrophilic functional group can be mixed well, for example, a block copolymer compatibilizer or a graft copolymer compatibilizer And preferably a graft copolymer compatibilizer can be 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 a mixture of a polyethylene-maleic anhydride graft copolymer or a polyethylene-glycidyl methacrylate graft copolymer in a polypropylene-maleic anhydride graft copolymer Can be used in one form.

The biodegradable resin composition for a three-dimensional printer filament according to the present invention may further contain other additives within the range not deviating from the intended use or effect, in addition to the main components described above. For example, it is possible to add various additives such as a nucleating agent, a heat stabilizer, a light stabilizer, a flame retardant, a carbon black, a pigment, an antioxidant and an impact modifier, May be added in the range of 0.1 to 10 parts by weight.

The molded article molded by the three-dimensional printing method using the biodegradable resin composition for a three-dimensional printer filament according to the present invention not only has excellent colorability but also has an improved impact strength. That is, the paintability grade according to the ASTM F 1842 evaluation method is 5 grade in acrylic paint, 4 grade or more in enamel paint and 5 grade in lacquer paint, and 3 grade with IZOD impact strength (ASTM D 256) of 8 kgf / cm or more It is possible to provide a biodegradable resin composition for a two-dimensional printer filament.

The biodegradable resin composition for a three-dimensional printer filament according to the present invention can be produced by a known melt extrusion method for producing a general resin composition. That is, a biodegradable resin, a polyolefin resin having at least one hydrophilic functional group, 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.

On the other hand, the resin composition molded from pellets can be extruded by a single-screw extruder at 170 to 200 ° C, cooled, rolled up, re-formed into filaments having a constant diameter, and used as 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) Biodegradable 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) 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.

(3) 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.

(4) Hydrophobic resin

Polypropylene (weight average molecular weight: 40,000) was used in the preparation of the resin composition according to the comparative example.

(5) Phenolic antioxidants

To prevent pyrolysis of the resin composition, Irganox 占^? Manufactured by Ciba Inc. ^? 1010 was used.

Example  One

, 10 parts by weight of a polyolefin resin having at least one hydrophilic functional group, 3 parts by weight of a compatibilizing agent, 0.1 phr of a phenolic antioxidant (0.1 part by weight based on 100 parts by weight of the total components excluding the additives), 90 parts by weight of a biodegradable resin, And extruded in a temperature range of 170 to 200 ° C in a twin-screw extruder having an L / D 25 and a diameter of 40 mm, and then extrudates were prepared in the form of pellets. The extruded pellets were dried at 80 DEG C for 12 hours.

Example  2

A pellet was prepared in the same manner as in Example 1, except that 80 parts by weight of the biodegradable resin and 20 parts by weight of the polyolefin resin having at least one hydrophilic functional group were mixed in Example 1.

Example  3

A pellet was prepared in the same manner as in Example 1 except that 70 parts by weight of the biodegradable resin and 30 parts by weight of the polyolefin resin having at least one hydrophilic functional group were mixed in Example 1.

Comparative Example  One

Pellets were prepared in the same manner as in Example 1 except that 100 parts by weight of the biodegradable resin was used without mixing the polyolefin resin having at least one hydrophilic functional group in Example 1.

Comparative Example  2

A pellet was prepared in the same manner as in Example 1 except that a hydrophobic resin was used instead of the polyolefin resin having at least one hydrophilic functional group in Example 1.

Comparative Example  3

A pellet was prepared in the same manner as in Example 2 except that a hydrophobic resin was used instead of the polyolefin resin having at least one hydrophilic functional group in Example 2.

Comparative Example  4

A pellet was prepared in the same manner as in Example 3, except that a hydrophobic resin was used instead of the polyolefin resin having at least one hydrophilic functional group in Example 3.

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  One

For evaluating the colorability of the resin composition for a three-dimensional printer filament according to the present invention, the resin compositions prepared according to the above Examples and Comparative Examples were subjected to a press molding (extraction after cooling at 190 캜 for 5 minutes and heating for 5 minutes) A specimen having a thickness of 3 mm was prepared, and the colorability was evaluated according to the following method. The results are shown in Figs. 2 to 4.

[Evaluation method of paintability]

Each of the prepared specimens was evaluated for colorability with reference to ASTM F1842. The paints were painted with appropriate pressure on the paintable specimens, dried naturally for 30 minutes, and cut into 25 grid shapes with a constant force using a cutting tool on the painted areas. Thereafter, the tape was uniformly applied to the painted area, and the tape was peeled off at a constant rate of 180 °, and the degree of peeling of the paint was observed and evaluated as shown in Table 3 below. As the above paints, acrylic paints (FLAT RED XF-7; TAMIYA AMERICA, INC.), Enalmel paints (BLACK X-1; TAMIWY INC.) And lacquer paints (Mr. Hobby / Gundam Mr. Color 2 - GLOSS BLACK ; GSI Creos Mr.Color) was used, and a 3M Scotch Multipurpose Tape (12 mm x 30 m) was used as the tape.

2 to 4, in the specimens (Examples 1 to 3) prepared by mixing the biodegradable resin and the resin having one or more hydrophilic functional groups in an optimum amount according to the present invention, the acrylic paint, the enamel paint and the lacquer paint It can be confirmed that the paint has excellent colorability in comparison with the comparative example. Specifically, in the case of the specimens prepared with the hydrophobic resin (Comparative Examples 2 to 4) instead of the resin having one or more hydrophilic functional groups, the specimens prepared from 100 parts by weight of the biodegradable resin (Comparative Example (Examples 1 to 3) prepared by mixing an optimal amount of a biodegradable resin and a resin having at least one hydrophilic functional group according to the present invention with less coloring than that of the biodegradable resin (5 to 15% delamination) to 5B (no delamination) in the case of acrylic paints and 1B grade (35 to 65% delamination) to 4B grades in the case of enamel type paints (Comparative Example 1) % Peeling), and that of the lacquer-based paint was improved from 4B (less than 5% peeling) to 5B (not peeling).

Test Example  2

In order to evaluate the physical properties of the resin composition for a three-dimensional printer filament according to the present invention, the resin compositions prepared according to Examples 1 to 3 and Comparative Example 1 were extruded at an injection machine (Dongshin Hydraulic Co., Ltd., Korea) having a mold clamping force of 150 tons After cooling for 80 seconds at 200 캜, the molded product was extrusion molded into ASTM test specimens. The prepared specimens were evaluated according to the ASTM standard and the results are shown in Table 4 below.

Referring to Table 4, in the case of the specimens (Examples 1 to 3) prepared by mixing the biodegradable resin and the resin having one or more hydrophilic functional groups in an optimum amount according to the present invention, biodegradation without mixing the resin having one or more hydrophilic functional groups The impact strength was remarkably improved to 224%, and the breaking point and HDT deterioration did not occur as compared with the specimen (Comparative Example 1) prepared with 100 parts by weight of the resin. 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.

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 (12)

(A) 50 to 95% by weight of a biodegradable resin; And
(B) 5 to 50% by weight of a polyolefin resin having at least one hydrophilic functional group for improving colorability;
And a biodegradable resin composition for a three-dimensional printer filament. The method according to claim 1,
Wherein the biodegradable resin is a biodegradable polyester resin produced by condensation polymerization of an aliphatic dicarboxylic acid, an aromatic dicarboxylic acid, or a mixture thereof with a diol compound. 3. The method of claim 2,
The biodegradable polyester resin may be at least one selected from the group consisting of polylactic acid (PLA), polybutylene succinate (PBA), polybutylenedi adipate-co-terephthalate (PBAT), polybutylene adipate-co-butylene terephthalate polybutylene glutarate-co-terephthalate (PHB), and polyhydroxybutyrate (PHB). The method according to claim 1,
Wherein the polyolefin resin has a hydrophilic functional group content of 0.1 to 10% by weight. The method according to claim 1,
Wherein the hydrophilic functional group is selected from the group consisting of acrylic, maleic anhydride, amine, carbonyl, hydroxyl and carboxyl. A biodegradable resin composition for a printer filament. The method according to claim 1,
Wherein the polyolefin resin is an ethylene vinyl acetate (EVA) resin having maleic anhydride as the hydrophilic functional group. The method according to claim 6,
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. The method according to claim 1,
A compatibilizer containing a block copolymer or a graft copolymer for forming a micro phase separation structure between the biodegradable resin and the polyolefin resin is added in an amount of 0.5 to 10 parts by weight per 100 parts by weight of the total of the biodegradable resin and the polyolefin resin Wherein the resin filaments have an average particle size of not more than 100 nm. 9. The method of claim 8,
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 resin is at least one selected from the group consisting of caprolactone polyester / poly (tetramethylene glycol) block polyol copolymer and methacrylate polystyrene copolymer. 9. The method of claim 8,
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 weight of the biodegradable resin composition. The method according to claim 1,
Wherein the composition has a degree of colorability according to the following evaluation method (ASTM F 1842) of 5 grades in an acrylic paint, 4 grades in an enamel paint, and 5 grades in a lacquer paint. Composition.
[Evaluation method of paintability]
Using this composition, a 3 mm thick paint sample was prepared with a press molding machine. The paint was painted on the specimen, dried and cut into 25 grid patterns using a cutting tool on the painted area, Tape, 3M) was evenly applied to the painted area and peeled off at an angle of 180 ° to evaluate the degree of peeling of the paint. The method according to claim 1,
Wherein the composition has an IZOD impact strength (ASTM D 256) of 8 kgf / cm or more.

Images