KR102544016B1 - Granular syringe filling composition for 3D printing, manufacturing method of composition and 3D printing ink manufacturing method - Google Patents

Abstract

According to the present invention, disclosed is a granular syringe filling composition for 3D printing, including a mixture of vegetable protein isolate and hydrocolloid dissolved in water, wherein the mixture is granulated. The present invention improves dispersibility and can output excellent 3D printing models.

Description

Granular syringe filling composition for 3D printing, manufacturing method of composition and 3D printing ink manufacturing method

The present invention relates to a granular syringe filling composition for 3D printing, a method for preparing the composition, and a method for preparing 3D printing ink.

Today, many consumers are reducing meat consumption and showing interest in healthy and sustainable food for various reasons, such as antibiotics in animal foods, cholesterol safety issues, health problems due to long-chain unsaturated fatty acids intake, and carbon emissions from meat consumption. Representatively, alternative foods prepared using vegetable proteins are being developed.

In particular, alternative foods are commercialized with 3D printing using vegetable proteins.

However, the use of 3D printers in the conventional food industry is still limited. In the prior art, ink for a 3D printer was directly filled into a syringe of a 3D printer to compress and output a 3D printed model. Here, since the gelated 3D printing ink is directly filled in the syringe, there is a problem that bubbles are mixed inside the syringe, and an additional process is required to eliminate this problem.

In addition, the gel causes water separation over a long period of time, causing a change in the moisture content in the gel and affecting physical properties and printability, so there is a limit to commercializing 3D printing models.

Republic of Korea Patent Publication 10-2019-0050472 Republic of Korea Patent Publication 10-2018-0051489 Korean Registered Patent No. 10-2353861 Republic of Korea Patent Publication 10-2016-0009067

The present invention provides a granular syringe-filling composition for 3D printing capable of improving water permeability and dispersibility by granulating powder of vegetable protein isolate, homogenizing gelation, and outputting an excellent 3D printing model, and the composition It is an object of the present invention to provide a manufacturing method and a 3D printing ink manufacturing method.

On the other hand, the technical problems to be achieved in the present invention are not limited to the above-mentioned technical problems, and other technical problems that are not mentioned will become clear to those skilled in the art from the description below. You will be able to understand.

A granular syringe filling composition for 3D printing according to an embodiment of the present invention includes a mixture of a vegetable protein isolate and a hydrocolloid dissolved in water, and granulates the mixture. .

In addition, the hydrocolloid is characterized in that pullulan (Pullulan).

In addition, the lysate is characterized in that the hydrocolloid is dissolved in water at a concentration of 1 to 5 (w / w)%.

In addition, the mixture includes the vegetable protein isolate and the lysate in a weight ratio of 50 to 60:40 to 50.

In addition, the granulation of the mixture is characterized in that, after kneading the vegetable protein isolate and the lysate, the dough is dried to produce granules.

In addition, it is characterized by drying the extruded product extruded through a sieve of 700 μm to 720 μm before drying the dough.

A method for preparing a granular syringe filling composition for 3D printing according to an embodiment of the present invention includes a mixing step of mixing a vegetable protein isolate and a hydrocolloid dissolved in water; A kneading step of kneading the mixture of the mixing step to prepare a dough; An extrusion step of extruding the dough through a sieve to produce an extrudate; and a drying step of drying the extrudate.

A 3D printing ink manufacturing method using a granular syringe filling composition for 3D printing according to an embodiment of the present invention includes a mixing step of mixing a vegetable protein isolate and a hydrocolloid dissolved in water; A kneading step of kneading the mixture of the mixing step to prepare a dough; An extrusion step of extruding the dough through a sieve to produce an extrudate; A drying step of drying the extrudate; and an ink preparation step of preparing a gelled 3D printing ink by mixing water with the dried material of the drying step.

In addition, the drying step is characterized in that the weight ratio of the water and the dried material is 1: 2.5 to 3.5.

According to an embodiment of the present invention, by granulating the powder of the vegetable protein isolate, water permeability and dispersibility can be improved, gelation can be made homogeneous, and an excellent 3D printing model can be output.

On the other hand, the effects obtainable in the present invention are not limited to the effects mentioned above, and other effects not mentioned will be clearly understood by those skilled in the art from the description below. You will be able to.

1 is a flow chart showing a method for preparing a granular syringe filling composition for 3D printing according to an embodiment of the present invention;
2 is a photograph showing the powder of Comparative Example 1 and the granules of Examples 1 to 4;
3 is a graph showing the storage modulus (G ') of Experimental Example 2;
4 is a graph showing the loss modulus (G") of Experimental Example 2;
5 is a graph showing storage modulus (G′) and loss modulus (G″) according to Experimental Example 3 of Example 5;
6 is a graph showing storage modulus (G ') and loss modulus (G ") according to Experimental Example 3 of Example 6;
7 is a graph showing storage modulus (G′) and loss modulus (G″) according to Experimental Example 3 of Example 7;
8 is a graph showing storage modulus (G′) and loss modulus (G″) according to Experimental Example 3 of Example 8;
9 is a photograph showing a 3D printed model according to Experimental Example 4.

Hereinafter, embodiments of the present invention will be described in more detail with reference to the accompanying drawings. Embodiments of the present invention may be modified in various forms, and the scope of the present invention should not be construed as being limited to the following examples. This embodiment is provided to more completely explain the present invention to those skilled in the art. Accordingly, the shapes of elements in the figures are exaggerated to emphasize clearer description.

The composition of the present invention for clarifying the solution to the problem to be solved by the present invention will be described in detail with reference to the accompanying drawings based on a preferred embodiment of the present invention, but the same reference numerals are assigned to the components of the drawings. For components, even if they are on other drawings, the same reference numerals have been given, and it is made clear in advance that components of other drawings can be cited if necessary in the description of the drawings.

A granular syringe filling composition for 3D printing, a method for preparing the composition, and a method for manufacturing 3D printing ink according to an embodiment of the present invention are a mixture of a vegetable protein isolate and a hydrocolloid dissolved in water. may contain mixtures.

In this case, the granular syringe filling composition for 3D printing may be granular to be granulated as a mixture, but is not limited thereto.

In addition, in the vegetable protein isolate, protein may be separated from any one of soybeans, peas, wheat, mung beans, and red beans.

In particular, pea protein isolates extracted from peas are used as food supplements for athletes and have excellent gel properties, dispersibility and fluidity. Accordingly, when mixing with a liquid such as water, it can be mixed uniformly.

Hydrocolloid refers to a polymer that exhibits viscosity by being hydrated and gelled. In more detail, hydrocolloid is a polysaccharide extracted from Auricularia auricula judae, and is used in the manufacture of various foods and beverages such as salad dressing, mayonnaise, and beverages, dental impression materials, and gauze for dressing.

An example of the hydrocolloid may be pullulan.

Pullulan is a food additive for increasing food stickiness and viscosity, enhancing emulsion stability, and improving physical properties and texture of food. As a substitute for gum arabic, pullulan gives products a soft touch and stabilizes the gel structure, so it is used in yokan, tofu, and stewed liquid. In particular, it has excellent film forming ability and is used for edible films.

That is, pullulan is an example of a hydrocolloid and is used as a solute in a solution for forming granules in the present invention.

In addition, the lysate may be a hydrocolloid, that is, pullulan dissolved in water at a concentration of 0.1 to 9 (w / w)%.

At this time, when preparing ink for 3D printing by mixing granules and water, when pullulan is dissolved at a concentration of 0.1 (w/w)% or less, it is prepared as 3D printing ink in a partially heterogeneous gel state, and the nozzle of the 3D printer This may be clogged, and the shape of the printed model may be uneven, resulting in deterioration in printability. In addition, when pullulan is dissolved at a concentration of 9 (w / w)% or more, it is possible to manufacture ink for 3D printing in a homogeneous gel state, but printability may deteriorate, such as collapsing or disorganizing the printed model after printing. can

In particular, when pullulan is dissolved in water at a concentration of 1 to 5 (w/w)%, an ink for 3D printing in a homogeneous gel state is prepared, and the printability is excellent because the printing model is not deformed after printing. can

Meanwhile, the mixture may include the vegetable protein isolate and the lysate in a weight ratio of 50 to 60: 40 to 50. At this time, it may be preferable to mix the vegetable protein isolate more than the lysate, but is not limited thereto.

In addition, when granulating the above-described mixture, after mixing and kneading the vegetable protein isolate and the lysate, the dough may be dried to prepare granules.

At this time, the granules may be formed in the form of pellets, but are not limited thereto.

When the pellet-type granules are filled into a syringe and react with water, the reacting surface area can be increased. In addition, water efficiently penetrates into the space between the granules to rapidly progress the reaction, and can be changed into a homogeneous gel.

In order to prepare such pellet-type granules, the extruded material extruded through a sieve of 700 μm to 720 μm may be dried before drying the dough.

On the other hand, referring to FIG. 1, the method for manufacturing a granular syringe filling composition for 3D printing according to an embodiment of the present invention includes a mixing step (S10), a kneading step (S20), an extrusion step (S30), and a drying step. (S40) may be included.

In the mixing step (S10), the vegetable protein isolate and the hydrocolloid may be mixed with the lysate dissolved in water.

At this time, the vegetable protein isolate may be prepared in a size of 300 μm or less. That is, the vegetable protein isolate can be prepared using a 300 μm sieve.

Further, the hydrocolloid may use pullulan, and the melt may be prepared by dissolving pullulan in water at a concentration of 1 to 5 (w/w)%.

In addition, the vegetable protein isolate and the lysate may be mixed in a weight ratio of 50 to 60:40 to 50. Preferably, it may be mixed in a weight ratio of 5:4, but is not limited thereto.

In the kneading step (S20), the mixture of the mixing step (S10) may be kneaded to prepare a dough.

In the extrusion step (S30), an extruded product may be produced by extruding the dough through a sieve.

At this time, an extrudate may be prepared by extruding through a sieve of 700 μm to 720 μm.

In the drying step (S40), the extrudate may be dried and granulated. The dried material, that is, the granular material thus prepared may be formed into pellets as it is extruded through a sieve.

On the other hand, the 3D printing ink manufacturing method using the granular syringe filling composition for 3D printing according to an embodiment of the present invention may include a mixing step, a kneading step, an extrusion step, a drying step, and an ink preparation step.

Here, in the 3D printing ink manufacturing method using the granular syringe filling composition for 3D printing, the mixing step, kneading step, extrusion step, and drying step are the same as the manufacturing method of the granular syringe filling composition for 3D printing described above. Detailed descriptions are omitted.

In the ink preparation step, 3D printing ink may be prepared by mixing water with the dried material in the drying step and gelling it.

At this time, the dry matter may be formed into pellet-type granules.

When the pellet-type granules are filled in a syringe and mixed with water, the pellet-type granules become gelated due to wetness, and 3D printing ink can be prepared.

At this time, as the granules are in the form of pellets, a gel-type 3D printing ink that is rapid and homogeneous can be produced by increasing the area where water is absorbed.

In addition, in the drying step, water and dried material may be mixed in a weight ratio of 1:2.5 to 3.5, preferably water and dried material may be mixed in a ratio of 1:3, but is not limited thereto.

Hereinafter, an experimental example examining the characteristics of a granular syringe filling composition for 3D printing will be described.

[Comparative Example 1]

The powder of the pea protein isolate was prepared by sieving the pea protein isolate through a 300 μm standard sieve.

[Example 1]

After preparing a lysate so that pullulan was dissolved in water at a concentration of 1 (w / w)%, it was mixed with the pea protein isolate of Comparative Example 1. At this time, 80 g of the lysate was mixed with 100 g of the pea protein isolate and homogeneously mixed for 10 minutes with a kneader to prepare a paste. Next, an extrudate was prepared by extruding through a standard sieve of 710 μm. And the extrudate was dried for 2 hours in a dry oven at 40 ℃. The dried granules were screened through a 1.0 mm standard sieve to have a length of 1.0 mm or more. However, when the length of granules did not exceed 1.0 mm, granules with a length smaller than 1.0 mm were used for comparison of properties.

[Example 2]

Granules were prepared in the same manner as in Example 1, but the concentration of pullulan in the lysate was 5 (w/w)%.

[Example 3]

Granules were prepared in the same manner as in Example 1, but the concentration of pullulan in the lysate was 9 (w/w)%.

[Example 4]

Granules were prepared in the same manner as in Example 1, but the concentration of pullulan in the lysate was 14 (w/w)%.

The prepared granules and powders of Examples 1 to 4 and Comparative Example 1 can be confirmed as shown in FIG. 2 . In addition, Example 1 with a low concentration of pullulan showed an appearance close to powder, and as the concentration of pullulan increased, granules appeared in the form of pellets.

[Experimental Example 1 - Measurement of density and cohesion]

After taking a picture of the prepared sample, the average length was confirmed using ImageJ software (NIH, Bethesda, MD, USA).

Next, Examples 1 to 4 and Comparative Example 1 were put into a 100 mL plastic mass cylinder, respectively, and the density and cohesion were measured by checking the weight versus volume.

In addition, the density was measured by [Equation 1] and [Equation 2] for bulk density and tap density, respectively. In addition, an ap density tester (JV 2000, Copley, England) was used to measure the tap density.

In addition, the cohesive force was measured by [Equation 3].

As shown in [Table 1], Examples 1 to 4 and Comparative Example 1 described above showed average particle length (mm), bulk density (%), tap density (%), and cohesive strength.

Average particle length (mm) Bulk Density (%) Tap Density (%) cohesion Comparative Example 1 - 31.02 ± 2.06 53.61 ± 1.69 1.73±0.06 Example 1 0.63 ± 0.29 36.16 ± 0.76 50.08 ± 2.51 1.38±0.05 Example 2 3.93 ± 0.59 20.55 ± 0.25 22.90 ± 0.31 1.11 ± 0.02 Example 3 7.42 ± 1.56 21.51 ± 0.23 22.99 ± 0.26 1.07 ± 0.02 Example 4 7.89 ± 1.71 23.08 ± 2.12 24.11 ± 2.58 1.04 ± 0.02

Referring to FIG. 1 and Table 1, since Comparative Example 1 was made of powder and had cohesiveness, empty areas occurred when filling the container. At this time, the bulk density is the density calculated by the volume of the particle volume and the space between the particles. Granulation can reduce the hollow area to be filled with more mass for the same volume. Accordingly, it was confirmed that Example 1 was filled with more mass due to a decrease in the hollow area in the same volume. And as the concentration of pullulan increased, the granules were pelletized and the bulk density decreased. Accordingly, it was confirmed that the concentration of pullulan dissolved in the lysate affected the formation and characteristics of granules.

In addition, the tap density represents the density calculated as the volume between the particles and the volume of the particles minimized through tapping. The tap density increased more than the bulk density. That is, it can be confirmed that the tap density increases as the particle size becomes smaller. And, when the granules have large particles (Examples 2, 3, and 4), the difference between the tap density and the bulk density was insignificant. This difference indicates that the granular layer inside the syringe can sufficiently withstand the impact of tapping.

In addition, it was confirmed that the granulation reduced the cohesive force, and the larger the size, the more the cohesive force was reduced.

[Experimental Example 2 - Dynamic Viscoelastic Properties of Examples 1 to 4 and Comparative Example 1]

For rheological properties, a rheometer (Paar Physica MCR 302, Anton Paar, Graz, Austria) equipped with a parallel plate with a diameter of 25 mm was used at 25 °C.

The gap between the probe and the plate was set to 1 mm, and vibration amplitude sweep measurements in the strain range of 0.1% to 100% confirmed the linear viscoelastic limit at a shear strain of 0.1%.

For dynamic viscoelastic properties, storage modulus (G') and loss modulus (G") were analyzed at an angular frequency of 1 to 100 rad/s. The results are shown in FIG. 3 (storage modulus (G')) and FIG. 4 (storage modulus (G ')), plotted on a logarithmic scale on both the x-axis and y-axis.

Referring to FIGS. 3 and 4, it can be seen that the values of G' and G" decrease as the concentration of pullulan used as the solution increases. This means that increasing the concentration of pullulan can reduce the dynamic viscoelasticity and result in insufficient mechanical properties for lamination.

Next, an experimental example examining the characteristics of 3D printing ink using a granular syringe filling composition for 3D printing will be described.

[Example 5]

The granules of Example 1 and water were mixed in a syringe at a weight ratio of 1:3.

[Example 6]

The granules of Example 2 and water were mixed in a syringe at a weight ratio of 1:3.

[Example 7]

The granules of Example 3 and water were mixed in a syringe at a weight ratio of 1:3.

[Example 8]

The granules of Example 4 and water were mixed in a syringe at a weight ratio of 1:3.

In Examples 5 to 8, it was confirmed that the granules became gels within 5 minutes after pouring water thereon.

[Comparative Example 2]

The powder of Comparative Example 1 and water were mixed in a syringe at a weight ratio of 1:3.

[Experimental Example 3 - Dynamic Viscoelastic Properties of Examples 5 to 8 and Comparative Example 1]

The dynamic viscoelastic properties were tested for the upper, middle and lower syringe points of Examples 5 to 8, and the experiment was conducted in the same manner as in Example 2.

Referring to FIGS. 5 to 8 , through dynamic viscoelasticity analysis of Examples 5 to 8, applicability of 3D printing ink to hydration and gelation to the top and bottom of the syringe was confirmed.

In particular, referring to FIG. 5 , Example 5 exhibited different characteristics according to the top, middle and bottom points of the syringe, and it can be seen that homogeneous gelation may not be achieved due to uneven swelling in the syringe. And inhomogeneous gelation can lead to clogging of nozzles. In addition, referring to FIGS. 6 to 8, Examples 6 to 8 showed a very small difference between the top, middle and bottom points of the syringe, which confirmed that homogeneous gelation was achieved as a whole.

That is, Examples 5 to 8 were suitable as food inks for 3D printers because the granules easily gel and form a homogeneous gel after being exposed to moisture. In addition, it was confirmed that pullulan allows water to easily penetrate into the granules.

[Experimental Example 4 - Evaluation of Printability of 3D Printing Ink]

Printability was evaluated after printing using a 3D printing-syringe-extrusion type 3D printer (YOLILO Co., Ltd.). At this time, the nozzle diameter is 1.1 mm. In addition, the printing model was a regular hexagon (length, width, height 15 mm) in order to confirm the breakage characteristics and continuity of the paste, and Examples 5 to 8 were printed.

Referring to FIG. 9, the 3D printing inks of Comparative Example 2 and Examples 5 to 8 were extruded smoothly and exhibited a shape similar to that of the input printed model.

In particular, Comparative Example 2 and Examples 5 and 6 maintained their shape until the end of the printing process. And no chemical bonding was observed between the pea protein isolate and pullulan.

In addition, in Examples 7 and 8, the phenomenon that the gel stretched or the bottom layer spread occurred.

It was confirmed that the 3D printing ink has an effect on the concentration of pullulan, and that printability decreases as the concentration of pullulan increases.

Referring to the above-described examples, the granules of Examples 1 and 3 were gelated after contact with moisture inside the syringe, and it was confirmed that the gelation was homogeneous through analysis of rheological properties. In addition, the 3D printing process confirmed the degree of shape retention after extrusion and lamination and the appropriate concentration of the binding solution. Here, since the granules of Example 1 may cause inhomogeneous gelation (see FIG. 5), preferably the granules of Example 3 can prepare an optimal 3D printing ink.

The above detailed description is illustrative of the present invention. In addition, the foregoing is intended to illustrate and describe preferred embodiments of the present invention, and the present invention can be used in various other combinations, modifications, and environments. That is, changes or modifications are possible within the scope of the concept of the invention disclosed in this specification, within the scope equivalent to the written disclosure and / or within the scope of skill or knowledge in the art. The written embodiment describes the best state for implementing the technical idea of the present invention, and various changes required in the specific application field and use of the present invention are also possible. Therefore, the above detailed description of the invention is not intended to limit the invention to the disclosed embodiments. Also, the appended claims should be construed to cover other embodiments as well.

S10: mixing step
S20: Kneading step
S30: extrusion step
S40: drying step

Claims (9)

A mixture of a vegetable protein isolate and a hydrocolloid dissolved in water; granulating the mixture,
The hydrocolloid is Pullulan,
In the lysate, the pullulan is dissolved in water at a concentration of 1 to 5 (w / w)%,
The granulation of the mixture is a granular syringe filling composition for 3D printing in which the vegetable protein isolate and the lysate are kneaded, and then the kneaded material is dried to produce pellet-type granules.
delete delete According to claim 1,
The mixture is a granular syringe filling composition for 3D printing comprising the vegetable protein isolate and the lysate in a weight ratio of 50 to 60: 40 to 50.
delete According to claim 1,
A granular syringe filling composition for 3D printing, characterized in that drying the extrudate extruded through a sieve of 700 μm to 720 μm before drying the dough.
A mixing step of mixing the vegetable protein isolate and the hydrocolloid dissolved in water;
A kneading step of kneading the mixture of the mixing step to prepare a dough;
An extrusion step of extruding the dough through a sieve to produce an extrudate; and
Including; drying step of drying the extrudate,
The hydrocolloid is Pullulan,
In the lysate, the pullulan is dissolved in water at a concentration of 1 to 5 (w / w)%,
In the drying step, a method for producing a granular syringe filling composition for 3D printing in which the extrudate is dried to prepare a pellet-type granulate.
A mixing step of mixing the vegetable protein isolate and the hydrocolloid dissolved in water;
A kneading step of kneading the mixture of the mixing step to prepare a dough;
An extrusion step of extruding the dough through a sieve to produce an extrudate;
A drying step of drying the extrudate; and
Including; an ink manufacturing step of preparing a 3D printing ink gelled by mixing water with the dried product of the drying step;
The hydrocolloid is Pullulan,
In the lysate, the pullulan is dissolved in water at a concentration of 1 to 5 (w / w)%,
In the drying step, 3D printing ink manufacturing method using a granular syringe filling composition for 3D printing in which the extrudate is dried to produce pellet-type granules.
According to claim 8,
The drying step is a 3D printing ink manufacturing method using a granular syringe filling composition for 3D printing in which the water and dry matter are in a weight ratio of 1: 2.5 to 3.5.

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