TWI837017B - Method of fixing 3d printed marks on substrates - Google Patents

Abstract

The present invention is a Method of fixing 3D printed marks on substrates. A polyester substrate is immersed in an aqueous solution of cetyltrimonium bromide to form a modified polyester substrate. The modified polyester substrate is then placed on one of the processing platforms of a 3D printer. Finally, a poly(lactic acid) and a poly(hydroxyl fatty acid ester) are mixed in the 3D printer and molded onto the surface of the modified polyester substrate according to a melt deposition molding method.

Description

3D printing method for solid substrate

The present invention relates to a method, in particular to a method for 3D printing a solid shape applied to a substrate.

Human beings have various needs such as food, clothing, housing, transportation, education, and entertainment. When they are full, they have to consider the issue of clothing. In the early stage, the basic functionality of clothing (warmth, breathability, comfort, etc.) was considered. In the later stage, In addition to gradually improving functionality, people nowadays pay more attention to style issues.

With the popularity of customization, all kinds of furniture, computer products and even personal belongings are gradually moving towards customization, and clothing has also become popular with customized logos (favorite patterns or styles, etc.) that can show personal style. .

At present, the most frequently used method is printing for decoration. Common special printing methods used for clothing fabrics include screen printing, thermal transfer printing, and ink printing. Inkjet printing has some disadvantages, such as slow printing speed, high cost of printing materials, etc.

Commonly used screen printing uses the volatilization of printing solvents or light-curing to solidify the ink, which often results in the surface hardness of the sign being too high and causing breakage. It is unable to present the three-dimensional sense of the sign, making it limited to flat decoration.

Furthermore, traditional screen printing inks (such as light curing) have a strong smell of solvent or ink, and often have a certain probability of leaving potential volatile organic matter residues on the clothing, and this production method is not environmentally friendly.

Furthermore, in addition to traditional screen printing, thermal transfer printing technology is also widely used. It uses transfer media such as transfer paper, transfer film, etc., and then transfers it through heat embossing using special thermal transfer equipment. Printed on the surface of the garment.

However, although the conventional thermal transfer machine structure can be used for imprinting semi-finished products (or materials), it is only suitable for semi-finished products (or materials). Thermal transfer printing technology cannot carry out partial embossing operations on a finished garment, such as on the shoulders of clothes, the outside of sleeves or the legs of trousers, so that the embossed pattern cannot achieve different decorative effects.

Later, although plasma surface treatment, high frequency welding and shaping logo technology can achieve three-dimensional logo technology, high frequency welding logo needs to open the plate or mold to make semi-finished products in advance, which will increase the cost of three-dimensional logo technology due to the cost of plate making and mold opening. In addition, high frequency welding technology requires a dedicated high frequency machine, and plasma surface treatment also requires a special machine for processing, so it is inconvenient to prepare.

Although embossed materials (sequins, beads or artificial diamonds) can be used to present a similar three-dimensional pattern, the biggest disadvantage of embossed materials is that the structure attached to clothing is too fragile and is easily affected by external stress or the pulling force of washing. And fall off.

Moreover, all embossed materials are manually pasted together, and the manufacturing process is extremely labor-intensive and time-consuming, thus increasing the production cost of the garments, which is reflected in the higher final selling price.

Therefore, how to make the logo on the fabric present a three-dimensional sense without increasing the cost is a problem that researchers in this technical field want to solve.

One purpose of the present invention is to provide a method for applying 3D printing to a solid form of a substrate. Polylactic acid and polyhydroxyalkanoate are mixed through 3D printing, and a three-dimensional sign is formed on the modified polyester. The surface of the substrate (modified by cationic surfactant) can be used to create a stable fabric on the polyester substrate without increasing the cost.

In view of the above-mentioned purpose, the present invention provides a method for 3D printing a solid substrate, wherein a polyester substrate is soaked in an aqueous solution of hexadecyltrimethylammonium bromide to form a modified polyester substrate, and then the modified polyester substrate is placed on a processing platform of a 3D printer. Finally, polylactic acid and a polyhydroxy fatty acid ester are placed in the 3D printer to mix and are formed on the surface of the modified polyester substrate according to a melt deposition molding method; wherein the molar concentration of the cationic surfactant solution is 0.01M.

The present invention provides an embodiment, which is a method for 3D printing a solid state applied to a substrate, wherein in the step of soaking a polyester substrate in an aqueous solution of hexadecyltrimethylammonium monobromide, the material of the polyester substrate is polyethylene terephthalate.

The present invention provides an embodiment, which is a method for 3D printing a solid applied to a substrate, wherein in the step of soaking a polyester substrate in an aqueous solution of hexadecyltrimethylammonium monobromide, the method further comprises the steps of: performing a pressure suction process on the polyester substrate under a pressure; and placing the polyester substrate in an oven and performing a drying process at 120-140°C.

The present invention provides an embodiment, which is a method for 3D printing a solid state applied to a substrate, wherein in the step of performing a suction process on the polyester substrate under a pressure, a suction machine is used.

The present invention provides an embodiment, which is a method for 3D printing a solid state applied to a substrate, wherein in the step of performing a pressure suction process on the polyester substrate under a pressure, the pressure is 0.8N/m2.

The present invention provides an embodiment, which consists in a method for applying 3D printing to a solid shape of a substrate, wherein in the step of placing the modified polyester substrate on a processing platform of a 3D printer, the modified polyester substrate is The high-quality polyester substrate is fixed on the processing platform through a colloid.

The present invention provides an embodiment, which is a method for 3D printing a solid state applied to a substrate, wherein in the step of placing the modified polyester substrate on a processing platform of a 3D printer, a preset temperature of the 3D printer is between 210°C and 230°C.

The present invention provides an embodiment, which is a method for 3D printing applied to a solid substrate, wherein in the step of forming on the surface of the modified polyester substrate according to a melt deposition molding method, a logo piece is formed on the surface of the modified polyester substrate.

The present invention provides an embodiment, which consists in a method of applying 3D printing to a solid shape of a substrate, wherein the marking component is a three-dimensional marking component or a planar marking component.

In order to enable you, the review committee, to have a further understanding of the characteristics and effects of the present invention, we would like to provide preferred embodiments and accompanying detailed descriptions, as follows:

Although the known heat transfer machine structure can be used for semi-finished products (or materials) to emboss, it is only for semi-finished products (or materials). Heat transfer technology cannot be used to perform partial embossing operations on a finished garment, such as on the shoulders of clothes, the outside of sleeves or the trouser legs of pants, so the embossed pattern cannot achieve different decorative effects.

Advantages of the present invention: The decorative effect of traditional logos on clothing is improved by mixing polylactic acid and polyhydroxy fatty acid esters through 3D printing, and forming a three-dimensional logo on the surface of a modified polyester substrate (modified by a cationic surfactant), thereby achieving a stable logo on the polyester substrate without increasing the cost, so that the logo is not easy to fall off or be torn.

Hereinafter, the present invention will be described in detail by illustrating various embodiments of the present invention with reference to the drawings. However, the concept of the present invention may be embodied in many different forms and should not be construed as being limited to the exemplary embodiments described herein.

First, please refer to Figure 1A, which is a flow chart of one embodiment of the present invention, and Figure 1B, which is a schematic structural diagram of a modified polyester base material with a logo element according to one embodiment of the present invention, as shown in Figure As shown, the steps of the method of applying 3D printing to the solid shape of the substrate in this embodiment are as follows:

Step S10: Soak the polyester base material in cetyltrimethylammonium bromide aqueous solution to form a modified polyester base material;

Step S20: Take the modified polyester base material and place it on the processing platform of the 3D printer; and

Step S30: Put polylactic acid and polyhydroxy fatty acid ester into the 3D printer to mix, and form them on the surface of the modified polyester substrate according to the melt deposition molding method.

In step S10, in this embodiment, a polyester substrate is immersed in an aqueous solution of hexadecyltrimethylammonium monobromide to form a modified polyester substrate 10, wherein the material of the polyester substrate is polyethylene terephthalate.

The molar concentration of the aqueous solution of hexadecyltrimethylammonium bromide used in this embodiment is 0.01 M. The aqueous solution of hexadecyltrimethylammonium bromide is a cationic surfactant.

The traditional surfactant is defined as follows: it is a substance that can significantly reduce the surface tension of a target solution, and can reduce the surface tension between two liquids or a liquid-solid. The most typical example is soap, which has the effect of decomposition and penetration and is widely used. The most common classification method of surfactants is based on the ionic form. This method is based on the fact that surfactants can dissociate into ionic forms when dissolved in water solvents. Ions or chemical changes that cannot be dissociated into ions are used as a basis to distinguish based on the type of ions generated. The use of the cationic surfactant solution in this embodiment means that the surfactant is dissolved in the aqueous solution and is connected to the surfactant after dissociation. The water-based part is in cationic form.

In step S10, please refer to FIG. 2, which is a schematic diagram of the processing flow of a polyester substrate according to an embodiment of the present invention. As shown in the figure, the steps include:

Step S12: performing a pressure suction process on the polyester substrate under pressure; and

Step S14: Take the polyester base material and place it in an oven at 120-140°C.

In this embodiment, a pressure is applied to the polyester substrate in the cetyltrimethylammonium bromide aqueous solution through a suction machine and a suction process is performed, so that the cetyltrimethylammonium bromide aqueous solution is The aqueous solution was fully absorbed by the polyester substrate, and the pressure was 0.8N/m ² .

The above-mentioned pressure absorption process is to pass the polyester substrate through the aqueous solution of hexadecyltrimethylammonium bromide and press it with a roller so that the aqueous solution of hexadecyltrimethylammonium bromide is fully absorbed in the polyester substrate, which can be divided into the process of immersing the polyester substrate in the aqueous solution of hexadecyltrimethylammonium bromide and the process of winding the liquid. The purpose of the pressure process is to make the aqueous solution of hexadecyltrimethylammonium bromide penetrate into the polyester substrate so that the aqueous solution of hexadecyltrimethylammonium bromide is uniformly attached to the polyester substrate.

Then, take out the polyester substrate that has been soaked in the cetyltrimethylammonium bromide aqueous solution, place the polyester substrate in an oven, and adjust the temperature of the oven to 120-140°C, so that the polyester substrate is The ester base material is subjected to a drying process in the oven, and the polyester base material after the drying process is completed is the modified polyester base material 10 .

Please refer to Figure 3, which is a Fourier transform infrared spectrum analysis diagram of one embodiment of the present invention. As shown in Figure 3, the modified polyester substrate (100% PET 150D/48F (B535/CTAB)), the unmodified polyester substrate (100% PET 150D/48F (B535) and the aqueous solution of hexadecyltrimethylammonium bromide were analyzed. As shown in Figure 3, the oscillation bands at 898 and 973 cm ^-1 belong to the left-handed and trans-formations of the oxyethylene group. Other important oscillation bands are those at 1340 and 1370 cm ^-1 , which are related to the trans- and left-handed conformations of _CH2 in the ester group of PET in the modified polyester substrate.

Finally, the third pair of bands characterizing the crystallinity of PET are the bands at ~1100 and ~1250 cm ^-1 , which are assigned to _{the torsion angles of the O=CO-CH2 ester groups} of PET. The band near 1740 cm ^-1 belongs to C=O carboxyl group. For the cetyltrimethylammonium bromide aqueous solution (CTAB), there are two obvious bands at 2917 cm ^-1 and 2850 cm ^-1 , which belong to asymmetric and symmetric methylene stretching vibrations respectively. It can be seen from the figure that the 2917 cm ^-1 and 2850 cm ^-1 of B535/CTAB are significantly increased and the surfactant is indeed impregnated. It proves that the polyester base material in this case has indeed been successfully modified into a modified polyester base material.

In this embodiment, as described in step S20, the modified polyester base material that has been modified is placed on a processing platform of a 3D printer, wherein the modified polyester base material is passed through A colloid is fixed on the processing platform, and the glue system uses lipstick glue or photo glue.

And a preset temperature on the processing platform is between 210°C and 230°C. The preset temperature is set to avoid warping of the printed matter placed on the processing platform. However, this embodiment uses The polyester substrate can therefore set the preset temperature and adjust the preset temperature to room temperature (about 23°C to 28°C).

Finally, in this embodiment, as described in step S30, a polylactic acid and a polyhydroxy fatty acid ester are placed in the 3D printer for mixing, and are molded on the surface of the modified polyester substrate according to a melt deposition molding method, so that a logo piece 20 is formed on the surface of the modified polyester substrate, wherein the logo piece 20 is a three-dimensional logo piece or a two-dimensional logo piece; for example: a logo on socks or a brand logo on a conventional sneaker.

Among them, the polylactic acid (PLA) used in this embodiment is a thermoplastic aliphatic polyester. Its raw material source is mainly plants such as corn, rather than petroleum compounds. It can be completely decomposed into water and carbon dioxide by microorganisms in the soil in a short period of time, and turned into starch by sunlight, which will not pollute the environment. It has the advantages of being biodegradable, not producing dioxin when burned, being similar to carbohydrates, and being non-toxic. The lactic acid or lactide required for the production of polylactic acid can be obtained by fermentation, dehydration, and purification of renewable resources. The obtained polylactic acid generally has good mechanical and processing properties, and the polylactic acid product can be quickly degraded in various ways after being discarded, which is very friendly to the environment.

The polyhydroxyalkanoate (PHA) is a polyester formed from natural sugar or paper through bacterial fermentation. It has good mechanical properties and processing properties, biodegradability and biocompatibility, and can be degraded in soil, seawater, fresh water, compost and other environments.

However, the disadvantage of the polylactic acid is that when the polylactic acid absorbs moisture in the air, it becomes brittle and easy to break. However, the polyhydroxyalkanoate has good mechanical properties and processing properties, biodegradability and biocompatibility. Therefore, in this embodiment, the polyhydroxyalkanoate (blended) is added to the polylactic acid to increase the mechanical strength after 3D printing, so that the polylactic acid mixed with the polyhydroxyalkanoate is molded on the modified polyester substrate. The surface of the sign will not be easily brittle and broken.

In addition, in this embodiment, the principle of the fused deposition molding method is to feed the thermoplastic filamentary material (the polylactic acid and the polyhydroxyalkanoate) to the hot melt nozzle, and heat and melt it in the nozzle. It is formed into filaments and then extruded. After rapid cooling, a thin layer of outline is formed on the modified polyester base material. When the cross-section shaping of one layer is completed, the next layer is cladded, and the cycle continues to form a three-dimensional sign. .

The traditional known thermal transfer mechanism cannot achieve different decorative effects. Although plasma surface treatment, high frequency welding and shaping sign technology have been developed in recent years to achieve three-dimensional signs, high frequency welding signs require the production of semi-finished products by opening a plate or mold in advance. The cost of plate making and mold opening will increase the cost of three-dimensional sign technology. In addition, high frequency welding technology requires a dedicated high frequency machine, and plasma surface treatment also requires a special machine for processing, so it is inconvenient to prepare.

The advantage of this embodiment is that polylactic acid and polyhydroxyalkanoate are mixed through 3D printing, and a three-dimensional sign is formed on the modified polyester substrate (through cetyltrimethylammonium bromide aqueous solution) Modification) surface, and then achieve a stable marking on the polyester substrate without increasing the cost, so that the marking is not easy to fall off or be torn.

And the hexadecyl trimethyl ammonium bromide (cetyltrimethylammonium bromide, CTAB for short) used in this embodiment is a long-chain hydrocarbon-based quaternary ammonium salt. CTAB is a cationic surfactant in the surfactant classification. The hydrocarbyl chain in its structure makes it have a strong attraction to hydrophobic molecules, and the quaternary ammonium salt cation in the structure is hydrophilic. This structure allows it to become a surfactant, turning the surface of hydrophobic substances into It is hydrophilic, so it will not cause the fabric to be toxic. Therefore, the modified polyester base material with the logo obtained in this embodiment will not affect the human body and produce toxicity.

Next, the following experimental group and control group are given to illustrate the difference in anti-peel strength between the polyester substrate without using the aqueous solution of hexadecyltrimethylammonium bromide to modify the polyester substrate and the polyester substrate with the aqueous solution of hexadecyltrimethylammonium bromide to modify the polyester substrate. The experimental conditions are as follows:

Control group:

1. Fabric used: 100% PET 150D/48F (referred to as B535);

2. The cetyltrimethylammonium bromide aqueous solution: not used;

3.3D printer: CR-10;

4. Nozzle temperature: 210℃, 220℃, 230℃; and

4. Wire: PLA/PHA wire, wire diameter 1.75mm, hardness 50D;

Experimental group:

1. Fabric used: 100% PET 150D/48F (abbreviated as B535);

2. The aqueous solution of hexadecyltrimethylammonium bromide: molar concentration 0.01M;

3.3D printer: CR-10;

4. Nozzle temperature: 210℃, 220℃, 230℃;

5. Wire: PLA/PHA wire, wire diameter 1.75mm, hardness 50D;

6. Pressure suction procedure: P-A0 pressure suction machine, operating pressure 0.8N/M ² ; and

7. Drying temperature: 130℃, 30 minutes.

After obtaining the polyester substrate with the logo piece and the modified polyester substrate with the logo piece under the above-mentioned control group and experimental group conditions, according to the test specification ASTM D1876: T-type peeling test, please refer to Figure 4, which is a schematic diagram of a T-type peeling test device of an embodiment of the present invention. As shown in the figure, an upper clamp 30 clamps the logo piece 20, and a lower clamp 40 clamps the polyester substrate/the modified polyester substrate 10, and pulls upward at a rate of 100 mm/min to detect the peeling strength between the printed object and the polyester substrate/the modified polyester substrate 10.

Please refer to FIG. 5 for the results of the anti-peeling strength, which is a schematic diagram of the peeling strength of an embodiment of the present invention. As shown in the figure, the peeling strength of the modified polyester substrate 10 is much greater than that of the unmodified polyester substrate. Therefore, it can be confirmed that the use of the aqueous solution of hexadecyltrimethylammonium bromide to modify the polyester substrate can effectively improve the state of the logo piece 20 falling off, and according to different nozzle temperatures, the anti-peeling strength of the logo piece 20 is greater. This is because at a higher temperature, PLA/PHA can more easily enter the modified polyester substrate 10, so that the logo piece can be more stably present on the surface of the modified polyester substrate 10.

In the embodiments described above, the method of the present invention is a method of applying 3D printing to a solid form of a substrate. Polylactic acid and polyhydroxyalkanoate are mixed by printing using a 3D printer, and The three-dimensional sign is molded on the surface of the modified polyester base material (modified by cetyltrimethylammonium bromide aqueous solution), thereby achieving a stable mark on the polyester base material without increasing the cost. parts so that the sign parts are not easy to fall off or be torn.

Therefore, this invention is novel, progressive and can be used in the industry. It should undoubtedly meet the patent application requirements of the Patent Law of our country. Therefore, we have filed an invention patent application in accordance with the law and pray that the Bureau will approve the patent as soon as possible. I am deeply grateful.

However, the above is only a preferred embodiment of the present invention and is not intended to limit the scope of implementation of the present invention. All equivalent changes and modifications made according to the shape, structure, features and spirit described in the patent application scope of the present invention should be included in the patent application scope of the present invention.

10: Modified polyester base material 20: Logo pieces 30: Upper clamp 40:Lower clamp S10: Steps S12: Steps S14: Steps S20: Steps S30: Steps

Figure 1A: It is a schematic diagram of the process of one embodiment of the present invention; Figure 1B: It is a schematic diagram of the structure of a modified polyester substrate with a logo piece of one embodiment of the present invention; Figure 2: It is a schematic diagram of the processing process of the polyester substrate of one embodiment of the present invention; Figure 3: It is an analysis diagram of the Fourier transform infrared spectrum of one embodiment of the present invention; Figure 4: It is a schematic diagram of a T-type peeling test device of one embodiment of the present invention; and Figure 5: It is a schematic diagram of the peeling strength of one embodiment of the present invention.

S10: Step

S20: Step

S30: Step

Claims (10)

A method for 3D printing solids applied to a substrate, comprising: Soaking a polyester substrate in an aqueous solution of hexadecyltrimethylammonium bromide to form a modified polyester substrate; Placing the modified polyester substrate on a processing platform of a 3D printer; and Mixing polylactic acid and a polyhydroxy fatty acid ester in the 3D printer, and molding them on the surface of the modified polyester substrate according to a melt deposition molding method. A method for applying 3D printing to a solid substrate as described in claim 1, wherein in the step of soaking a polyester substrate in an aqueous solution of hexadecyltrimethylammonium monobromide, the material of the polyester substrate is polyethylene terephthalate. A method for applying 3D printing to a solid substrate as described in claim 1, wherein in the step of soaking a polyester substrate in an aqueous solution of hexadecyltrimethylammonium bromide, the molar concentration of the aqueous solution of hexadecyltrimethylammonium bromide is 0.01M. The method of applying 3D printing to the solid form of a substrate as described in claim 1, wherein the step of soaking a polyester substrate in an aqueous solution of cetyltrimethylammonium bromide further includes the following steps: Perform a suction process on the polyester substrate under a pressure; and Take the polyester base material and place it in an oven at 120-140°C. A method for applying 3D printing to a solid substrate as described in claim 4, wherein in the step of performing a suction process on the polyester substrate under a pressure, a suction machine is used. The method for applying 3D printing to a solid substrate as described in claim 4, wherein in the step of performing a pressure suction process on the polyester substrate under a pressure, the pressure is 0.8 N/m ² . A method for applying 3D printing to a solid substrate as described in claim 1, wherein in the step of placing the modified polyester substrate on a processing platform of a 3D printer, the modified polyester substrate is fixed on the processing platform by a colloid. A method for applying 3D printing to a solid substrate as described in claim 1, wherein in the step of placing the modified polyester substrate on a processing platform of a 3D printer, a preset temperature of the 3D printer is between 210°C and 230°C. The method for applying 3D printing to the solid shape of a base material as described in claim 1, wherein in the step of forming on the surface of the modified polyester base material according to a fused deposition molding method, the modified polyester base A marking piece is formed on the surface of the material. The method of applying 3D printing to a solid shape of a substrate as described in claim 9, wherein the marking component is a three-dimensional marking component or a flat marking component.

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