TWI641569B - Manufacturing method of three-dimensional ceramic glass and composition thereof - Google Patents

Abstract

The present invention relates to a method for manufacturing a three-dimensional printing of a ceramic glass molding, comprising: outputting layer data of a workpiece to be formed by a three-dimensional printing device; and three-dimensional printing equipment performing layer analysis according to the layer data, using a low temperature ceramic glass composition and a transparent glue And the full-color ink layer stacks the three-dimensional ceramic glass semi-finished product; the ceramic glass semi-finished product is dried; and the ceramic glass semi-finished product is subjected to a thermal conversion process to form a ceramic glass molded product.

Description

Three-dimensional printing method for ceramic glass molding and composition thereof

The present invention relates to a ceramic glass molded article, and more particularly to a three-dimensional printing method for a ceramic glass molded article and a composition thereof.

With the development of three-dimensional printing technology, the types of materials that can be used in three-dimensional printing are becoming more diverse, such as metals, polymers, ceramics and the like. Commonly used polymer materials such as ABS resin, epoxy resin (Epoxy), etc., are low-temperature easy-formable materials, that is, they can be three-dimensionally printed at a lower temperature, while materials such as metals and ceramics are formed at a high temperature. The material, that is, it needs to be at a high temperature for three-dimensional printing. In the traditional methods of the past, the crystal, glass, ceramics, enamel molding and sheet metal processes, etc., the production process is quite complicated and not environmentally friendly, and all of them require multiple high-temperature processes to be fired or carried out. It is quite dangerous for the manufacturer. Therefore, if ceramic glass can be produced in a three-dimensional printing manner, the conventional technology will be considerably improved.

Although there have been conventional techniques for three-dimensional printing of glass in the past, the conventional technology is limited by technology, and the finished products are only monochromatic glass, and a large amount of gas is generated during the printing process, and the fineness of the finished product. It is also not good, and there are no related improvements in technology. Another related conventional technique is similar to the extrusion molding method of polymer extrusion type, which uses the furnace body to melt the glass first, and then controls the flow of the high temperature glass paste to perform three-dimensional printing. The technology, however, is limited to the high temperature process of the prior art, and the finished product can only be monochromatic, and in the prior art, since the glass needs to be heated to a molten state, the processing temperature exceeds 1100 ° C, and the high temperature is operated. It is relatively dangerous for personnel, and because this prior art uses glass paste for three-dimensional printing, the viscosity of the glass paste is high and the control is not easy. Therefore, the finished product produced by the prior art process cannot be refined, and thus cannot be printed. Out of the fine glass products.

Therefore, how to develop a three-dimensional printing method for ceramic glass moldings and a composition thereof, and in the prior art, the finished glass products produced by the three-dimensional printing method are all monochromatic, and the manufacturing process is a high-temperature process. The problem of poor fineness of the finished product is an urgent problem to be solved in the field.

The main purpose of the present invention is to provide a three-dimensional printing method for ceramic glass moldings and a composition thereof. In the prior art, the finished glass products produced by the three-dimensional printing method are all monochromatic, and the manufacturing process is high temperature. The process and the poor quality of the finished product.

In order to achieve the above object, the present invention provides a method for manufacturing a three-dimensional printing of a ceramic glass molded article, comprising: outputting layer data of a workpiece to be formed by a three-dimensional printing device; and the three-dimensional printing device performs a layer analysis according to the layer data to low temperature. The ceramic glass composition, the transparent glue and the full-color ink layer stack printed the ceramic glass semi-finished product; the ceramic glass semi-finished product was dried; and the ceramic glass semi-finished product was subjected to a thermal conversion process to form a ceramic glass molded product.

In order to achieve the above object, the present invention further provides a composition of a ceramic glass molding, comprising: a low temperature ceramic glass composition, which is composed of a bismuth compound and a bonding agent, and the low temperature ceramic glass composition is at 300 to 400 ° C. Formed at a temperature; a transparent glue comprising a nonionic surfactant, a polyol compound having two or more hydroxyl groups, an ether alcohol compound having a linear chain of 1 to 4 carbons, an antibacterial agent, Ionic water and binder; and a full-color ink containing nonionic surfactant, a polyol compound with two or more hydroxyl groups, an ether alcohol compound with one to four carbon straight chains, and an antibacterial agent Agent, deionized water, aqueous pigment dispersion and pigment stabilizer.

Some exemplary embodiments embodying the features and advantages of the present invention are described in detail in the following description. It is to be understood that the present invention is capable of various modifications in various embodiments, and is not intended to limit the scope of the invention.

Please refer to FIG. 1 , which is a flow chart of a three-dimensional printing method for a ceramic glass molded article according to a preferred embodiment of the present invention. As shown in the figure, the three-dimensional printing method for the ceramic glass molded article of the present invention first provides a three-dimensional printing device, and then, according to step S11, the layer material of the object to be formed is first output through the three-dimensional printing device. Then, as described in step S12, the three-dimensional printing device performs a layer analysis according to the layer data to analyze the contour of each layer, and then prints the low temperature ceramic glass composition, the transparent glue and the full color. The ink is further printed in a layer stack to print a three-dimensional ceramic glass semi-finished product, wherein the low-temperature ceramic glass composition is formed at a temperature of 300 to 400 ° C, but not limited thereto, and can be adjusted according to actual needs. The proportion of each component in the low-temperature ceramic glass composition is adjusted to the actual required molding temperature, and the water-based environmentally-friendly pigment of the full-color ink is added through the printing process, and the molding temperature of the low-temperature ceramic glass composition is controlled at 300 to 400. Forming between °C, and then printing transparent glue to form a printed semi-finished ceramic glass, so that the water-based environmentally-friendly pigment in the full-color ink can be coated on the low-temperature ceramic glass composition. At this time, the ceramic glass semi-finished product needs to undergo a thermal conversion process before it can be converted into ceramic glass, so then the ceramic glass semi-finished product is dried in the shade as described in step S13, thereby removing excess water for the subsequent thermal conversion process. . Finally, as described in step S14, the ceramic glass semi-finished product is subjected to a thermal conversion process to form a ceramic glass molded product, wherein, in the thermal conversion process, the ceramic glass semi-finished product is heated to a glass transition temperature and converted into a three-dimensional ceramic glass molding. Things.

In this case, the full-color ink is added to the printing process through the three-dimensional printing equipment, and the molding temperature of the low-temperature ceramic glass composition is controlled to be formed between 300 and 400 ° C, and then the combination of transparent glue is printed, thereby making the full color The environmentally friendly water-based pigment in the ink is coated on the low-temperature ceramic glass composition to overcome the problem that the conventional ceramic glass forming is complicated in glass conversion coloration, and can be converted with the thermal conversion procedure before the allowable temperature carbonization of the aqueous pigment disappears. It is a full-color ceramic glass molding, and the ceramic glass molding can have a variety of colors.

In this way, in the three-dimensional printing process of the ceramic glass molding in the present case, the ceramic glass semi-finished product can be automatically printed in three dimensions through the three-dimensional printing device, and through the subsequent simple dry and hot conversion process, that is, It can produce full-color ceramic glass moldings in a low-temperature process, and it does not require a lot of manpower, and the process is relatively simple and efficient, and at the same time, it can effectively save production time. Compared with the traditional glass method, the case can have the same color bonding as the traditional method, retain the special structure of the finished product, and have high-quality optical properties (such as absorption/transparency), and can It is carried out in a fast and safe manner, and compared to the conventional glass three-dimensional printing technology, the present invention can print ceramic glass moldings with high fineness and color, and can be carried out at a lower temperature. Moreover, compared with the conventional glass three-dimensional printing technology, it is required to be carried out in a temperature environment exceeding 1100 ° C. This case is a relatively low temperature process, so it is relatively safe for the operator.

The composition of the ceramic glass molding of the present invention is a molding material which can be used for three-dimensional printing to print a ceramic glass molding, and the composition of the ceramic glass molding comprises a low-temperature ceramic glass composition, a transparent glue and a full-color ink. .

The low-temperature ceramic glass composition is composed of a bismuth compound-bonding agent, and the low-temperature ceramic glass composition can be molded at 350±50° C. (300° C. to 400° C.) and has a particle size of 80 μm or less and can be selected. The products currently on the market are not limited to this. Wherein, the citrate compound is at least one of a group consisting of quartz (SiO2), feldspar (also known as marblerite), and china clay (also known as kaolin); the binder is selected from a water-soluble polymer, which can be synthesized. The composition or the natural composition is not limited thereto, and the adhesive is polyvinyl alcohol, polyvinylpyrrolidone, gum arabic, seaweed gum, dextrin, gelatin and starch (eg, amylose, amylopectin) At least one of the group consisting of 2 to 20% by weight of the total amount of the low-temperature ceramic glass composition is preferably 5 to 12% by weight based on the total amount of the low-temperature ceramic glass composition.

The transparent glue contains a nonionic surfactant, a polyol compound having two or more hydroxyl groups, an ether alcohol compound having one to four carbon straight chains, an antibacterial agent, deionized water, and a binder, but Not limited to this. Non-ionic surfactants use Ethoxylated Acetylenic Diol type nonionic surfactants, such as Surynol 440, Surynol 465, and Surynol 485, which account for 0.5-2% by weight of transparent glue; The polyol compound of two or more hydroxyl groups is composed of 1,3-/1,2-propanediol, 1,4-/1,3-/1,2-butanediol, 1,5-/1,4 At least one of the group consisting of -/1,3-/1,2-pentanediol, trimethylolpropane, trimethylolethane, glycerol, pentaerythritol and sorbitol, accounting for 2 of the total amount of transparent glue ~ 20% by weight; a linear ether alcohol compound having 1 to 4 carbons is at least one of a group consisting of diethylene glycol ether, triethylene glycol ether and tetraethylene glycol ether. The total amount of the transparent glue is less than or equal to 5% by weight, and the total amount of the polyol compound and the ether alcohol compound is not more than 20% by weight based on the total amount of the transparent glue; the water-soluble polymer is selected as the binder; The composition or the natural composition is not limited thereto, and the adhesive is made of polyvinyl alcohol, polyvinylpyrrolidone, gum arabic, seaweed gum, dextrin. At least one of the group consisting of gelatin and starch (eg, amylose, branched starch) accounts for 0.5 to 5 weight percent of the total amount of transparent glue, and is 0.5 to 2 weight percent of the total amount of transparent glue. Good; antibacterial agent selected Proxel GXL or BIT 20, accounting for 0.1 ~ 1% by weight of transparent glue; deionized water accounted for 80 ~ 90% by weight of transparent glue.

Full color ink contains nonionic surfactant, polyol compound with two or more hydroxyl groups, ether alcohol compound with one to four carbon straight chains, antibacterial agent, deionized water, water pigment dispersion Liquid and pigment stabilizers, but not limited to this. Non-ionic surfactants use Ethoxylated acetylenic diol type nonionic surfactants, such as Surynol 440, Surynol 465, and Surynol 485, which account for 0.1 to 2% by weight of the total color ink. Avoiding more than 2% by weight will allow the glue to penetrate the powder layer too quickly or smudge to the surrounding color, resulting in unclear bleaching between the color and color; with 1 to 4 carbon straight chains The ether alcohol compound is composed of diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether. a group consisting of ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monopropyl ether and triethylene glycol monobutyl ether At least one of them accounts for 5 to 15% by weight of the total color ink; the polyol compound with two or more hydroxyl groups is composed of 1,3-/1,2-propanediol, 1,4-/1 , 3-/1,2-butanediol, 1,5-/1,4-/1,3-/1,2-pentanediol, trimethylolpropane, trimethylolethane, glycerol, pentaerythritol and a group of sorbitol One of the less, accounting for 10 to 30% by weight of the total color ink, the polyol compound is mainly used as a moisturizer in the glue and can improve the stability of the ink; the antibacterial agent is Proxel GXL or BIT 20, which accounts for the total color ink. Amount of 0.1 to 1% by weight; aqueous pigment dispersion, using commercially available products, accounting for 10 to 30% by weight of total color inks, such as Cabot's COJ series, Clariant's HostaJet PT series, and various other pigment dispersions available. , including black / positive red / blue / magenta / cyan / yellow / green; pigment stabilizers use nitrogen-containing heterocyclic compounds, nitrogen-containing heterocyclic compounds are composed of pyrrolidone, methylpyrrolidone and pyrrolidone At least one of the groups accounts for 2 to 10% by weight of the total color ink; deionized water accounts for 50 to 80% by weight of the total color ink.

The following describes the implementation of the transparent glue and full color ink of the preferred embodiment of the present invention:

Table 1 Transparent glue of the preferred embodiment of the present invention

Table 2 Full color ink of the preferred embodiment of the present invention

Table 3: Full color ink of another preferred embodiment of the present invention

In this case, the water-based environmentally-friendly pigment of full-color ink is added in the printing process, and the molding temperature of the low-temperature ceramic glass composition is controlled to be formed between 300 and 400 ° C, and then the transparent glue is sprayed to form a semi-finished ceramic glass. The water-based environmentally-friendly pigment in the full-color ink can be coated on the low-temperature ceramic glass composition for the thermal conversion process, and the thermal conversion process of the present invention will be printed before the carbonization of the pigment is allowed to disappear. The glass transition is achieved and the color state can be maintained after the thermal conversion process.

In summary, the three-dimensional printing method and composition of the ceramic glass molded article provided by the present invention are formed by using a three-dimensional printing device, a low-temperature ceramic glass composition, a transparent glue and a full-color ink as a molding material, and then layered. Stacking and printing a three-dimensional ceramic glass semi-finished product, and then through the dry and hot conversion process to form a ceramic glass molding, through which the three-dimensional printing technology can automatically and efficiently form a full-color three-dimensional ceramic glass semi-finished product. The ceramic glass molding obtained by the thermal conversion has a plurality of colors, and does not need to perform complicated coloring procedures as in the conventional glass manufacturing process, and can maintain the advantages of high fineness and good optical quality in the conventional glass manufacturing process. Moreover, compared with the conventional glass three-dimensional printing technology, the finished products are all monochromatic, and the process temperature is high. The ceramic glass molding of the present invention can have multiple colors and low process temperature, so it can be compared with the prior art. , used in a wider range of fields, such as art, building materials, personalized goods, biomedical fields and so on. Therefore, the three-dimensional printing method and composition of the ceramic glass molded article of the present invention have great industrial utilization value, and the application is made according to law.

This case has been modified by people who are familiar with this technology, but it is not intended to be protected by the scope of the patent application.

S11, S12, S13, S14‧‧ steps

1 is a flow chart showing a method for manufacturing a three-dimensional printing of a ceramic glass molded article according to a preferred embodiment of the present invention.

Claims (25)

A three-dimensional printing method for manufacturing a ceramic glass molded article, comprising: (a) outputting a layer material of a shape to be formed by a three-dimensional printing device; and (b) performing a layer analysis on the three-dimensional printing device according to the layer data; Forming a three-dimensional ceramic glass semi-finished product by a low-temperature ceramic glass composition, a transparent glue and a full-color ink layer stack, wherein the low-temperature ceramic glass composition is formed at a temperature of 300 to 400 ° C; (c) Drying the ceramic glass semi-finished product; and (d) performing a thermal conversion process on the ceramic glass semi-finished product to form a ceramic glass molded product, wherein the thermal conversion process is performed in three-dimensional heating of the ceramic glass semi-finished product to a glass transition temperature get on. A ceramic glass molding composition comprising: a low temperature ceramic glass composition comprising a bismuth compound and a binder, the low temperature ceramic glass composition being formed at a temperature of 300 to 400 ° C; a transparent glue , comprising a nonionic surfactant, a polyol compound having two or more hydroxyl groups, an ether alcohol compound having a linear chain of 1 to 4 carbons, an antibacterial agent, deionized water, and a binder; Full color ink, including nonionic surfactant, polyol compound with two or more hydroxyl groups, ether alcohol compound with 1 to 4 carbon linear chains, antibacterial agent, deionized water, water-based pigment Dispersion and pigment stabilizers. The composition of the ceramic glass molded article according to claim 2, wherein the phthalate compound is at least one of the group consisting of quartz, feldspar and china clay. The composition of the ceramic glass molding according to claim 2, wherein the binder is a water-soluble polymer, which is composed of polyvinyl alcohol, polyvinylpyrrolidone, gum arabic, seaweed gum, dextrin, gelatin and At least one of the groups consisting of starch. The composition of the ceramic glass molding according to claim 4, wherein the binder of the low temperature ceramic glass composition accounts for 2 to 20% by weight of the total. The composition of the ceramic glass molded article according to claim 4, wherein the binder of the low-temperature ceramic glass composition is preferably 5 to 12% by weight based on the total amount of the low-temperature ceramic glass composition. The composition of the ceramic glass molding according to claim 4, wherein the adhesive of the transparent glue accounts for 0.5 to 5 weight percent of the total amount of the transparent glue. The composition of the ceramic glass molding according to claim 4, wherein the adhesive of the transparent glue is preferably 0.5 to 2% by weight based on the total amount of the transparent glue. The composition of the ceramic glass molded article according to claim 2, wherein the total amount of the polyol compound and the ether alcohol compound in the transparent glue is not more than 20% by weight based on the total amount of the transparent glue. The composition of the ceramic glass molded article according to claim 2, wherein the nonionic surfactant is selected from Ethoxylated acetylenic diol. The composition of the ceramic glass molding according to claim 10, wherein the non-ionic surfactant of the transparent glue accounts for 0.5 to 2% by weight of the total amount of the transparent glue. The composition of the ceramic glass molded article according to claim 10, wherein the non-ionic surfactant of the full-color ink accounts for 0.1 to 2% by weight of the total amount of the full-color ink. The composition of the ceramic glass molding according to claim 2, wherein the polyol compound having two or more hydroxyl groups in the transparent glue accounts for 2 to 20% by weight of the total amount of the transparent glue. The composition of the ceramic glass molding according to claim 2, wherein the polyol compound having two or more hydroxyl groups in the full color ink accounts for 10 to 30% by weight of the total color ink. . The composition of the ceramic glass molded article according to any one of claims 13 to 14, wherein the polyol compound having two or more hydroxyl groups is 1,2-propanediol and 1,3-propanediol. 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 1 At least one of the group consisting of 5-pentanediol, trimethylolpropane, trimethylolethane, glycerol, pentaerythritol, and sorbitol. The composition of the ceramic glass molding according to claim 2, wherein the linear ether alcohol compound having 1 to 4 carbons of the transparent glue accounts for less than 5 weight percent of the total amount of the transparent glue. The composition of the ceramic glass molded article according to claim 2, wherein the ethereal alcohol compound having 1 to 4 carbon linear chains of the transparent glue accounts for 5 wt% of the total amount of the transparent glue. The composition of the ceramic glass molding according to claim 2, wherein the full-color ink has an ethereal alcohol compound having 1 to 4 carbon linear chains, and the total amount of the full-color ink is 5 to 15 weight. percentage. The composition of the ceramic glass molded article according to any one of claims 16, wherein the linear ether alcohol compound having 1 to 4 carbons is diethylene glycol ether or the like. One of a group consisting of glycol ethers and tetraethylene glycol ethers. The composition of the ceramic glass molding according to claim 2, wherein the antibacterial agent accounts for 0.1 to 1% by weight of the total amount of the transparent glue. The composition of the ceramic glass molding according to claim 2, wherein the antibacterial agent accounts for 0.1 to 1% by weight of the total amount of the full color glue. The composition of the ceramic glass molded article according to claim 2, wherein the aqueous pigment dispersion accounts for 10 to 30% by weight of the total amount of the full color glue. The composition of the ceramic glass molding according to claim 2, wherein the pigment stabilizer accounts for 2 to 10% by weight of the total color of the full color glue. The composition of the ceramic glass molding according to claim 23, wherein the pigment stabilizer is a nitrogen-containing heterocyclic compound. The composition of the ceramic glass molded article according to claim 24, wherein the nitrogen-containing heterocyclic compound is at least one of the group consisting of pyrrolidone, methylpyrrolidone and pyrrolidone.