JP2018199864A - Method for producing laser-sintering metallic colloid - Google Patents

Abstract

To provide a laser-sintering metallic colloid, and to provide a method for producing the same.SOLUTION: A laser-sintering metallic colloid is formed by dispersing metallic material powder uniformly on a polymer comprising bisphenol A ethoxylate (BPA-EO), xylene, and polyoxyethylene fatty acid ester. The laser-sintering metallic colloid of this invention is to be provided directly in a region to be repaired of a workpiece when applied to 3D printing, whereby it can solve such problems as blowing away powder due to conventional 3D printing, eliminates the need for additional installation of a powder-collecting system, reduces the usage and waste of a metal powder, and reduces a processing cost.SELECTED DRAWING: None

Description

  The present invention relates to a metal colloid for laser sintering modeling and a manufacturing method thereof. In particular, a metal colloid for laser sintering modeling formed by uniformly dispersing a metal material powder in a polymer composed of bisphenol A ethoxylate (BPA-EO), xylene, and polyoxyethylene fatty acid ester, and this laser firing The present invention relates to providing a method for producing a metal colloid for shaping.

  3D printing technology is rapid prototyping (RP), which can reduce R & D costs, shorten the development cycle, increase the success rate of new product development, as well as the needs of individual production and local manufacturing It has excellent functions such as satisfying the requirements. Since the rapid development since the 1980s, technologies, equipment, processes and methods related to 3D printing have continued to develop dramatically, and the types, models and types of 3D printing machines have evolved innovatively. In addition, the quality, speed, size, and output stability associated with 3D printing have been greatly improved. Over the past decade, the 3D printing market has expanded and grown dramatically.

  In general, 3D printing modeling technology automatically uses a technology concept that builds up pyramids one after another without using tools, dies or jigs, and automatically creates patterns with complex design shapes. It is a rapid prototyping technique that can be quickly and rapidly made into a three-dimensional solid shape. In other words, 3D printing is based on the principles of layer cutting, stacking, and deposition manufacturing, and a modeling material containing components such as specific plastics, metals, etc. that have been made into a solution, solvated or melted on one flat surface. While forming a two-dimensional plane of the XY axis by ink jet printing precisely and directly with a 3D printing device, by adding light energy, electrical energy, chemical energy, sintering, sticking, drying, solidifying, Z Positioning and stacking accurately while moving in the axial direction, a three-dimensional solid body is finally formed.

  Conventionally, in 3D printing, fused deposition molding (FDM; also called Fused Filament Fabrication, FFM), laminate manufacturing (Laminated Object Manufacturing, LOM), digital light processing, digital light processing, digital light processing (LIM), digital light processing, digital light processing (FIM). FTI), stereolithography equipment (Stereo-lithography Apparatus, SLA), adhesive-cured 3D printing (Poster-based 3D printing, Powder bed and ink jet head 3D printing, 3DP), selective laser sintering ive Laser Sintering, SLS), selected laser melting (Selective Laser Melting, SLM; a or Direct Metal Laser Sintering, referred to as DMLS) generally used three-dimensionally shaped technique such.

  However, among the above-described conventional 3D printing, particularly in the method of forming a metal three-dimensional structure, since it is necessary to adjust the composition of the binder according to the metal powder to be used, the manufacturing cost is increased, and further 3D printing work is performed. In this case, a solid material having a desired three-dimensional shape cannot be obtained by a chemical reaction between the binder itself or the binder and the metal powder. As a result, the material cannot be recycled and needs to be discarded.

  In addition, when printing metal parts in conventional 3D, the movement position of the metal powder cannot be accurately specified, and there is a problem that the strength of the metal parts varies. Can use only one metal powder. In order to avoid breakage of the nozzle due to the binder or the metal powder, it is often necessary to perform printing using a piezoelectric nozzle, which increases the cost.

  On the other hand, in the conventional 3D printing method, the metal powder is not applied to repair of metal parts, but is generally used for manufacturing metal parts. In addition, since metal powder cannot normally be arrange | positioned perpendicular | vertical to the cross section of an object, the cross section of the metal component which should be repaired cannot be repaired smoothly.

  In addition, repairs to metal parts having a three-dimensional structure are often impossible when parts or all of the parts are not disassembled or updated. As a result, there is a problem that the cost of metal processing is increased, and a metal part having a breakage or a defect or a defective metal product cannot be repaired precisely.

  Therefore, in order to solve the problems of the prior art, the metal colloid for laser sintering modeling that can solve problems such as inconvenience in actual use, wasteful use of raw materials, and high manufacturing costs. There is an urgent need to develop a method for manufacturing the same.

  Therefore, as a result of intensive investigations to solve the problems of the prior art, the present inventors can not only improve the above-mentioned disadvantages of the prior art, wasteful use of raw materials, and increased manufacturing costs, but also improve the parts. By developing a new technology capable of repairing a three-dimensional structure without disassembling or updating, and in particular, repairing a damaged or defective metal part or defective metal product precisely, the present invention It reaches.

  That is, the present invention is a method for producing a metal colloid for laser sintering modeling, wherein (a) 500 to 2000 parts by weight of bisphenol A ethoxylate (BPA-EO) and 0.25 to 2 parts by weight of catalyst are added to 140 parts. For 4 to 8 hours at a temperature of from ℃ to 180 ℃, then add 200 to 800 parts by weight of xylene, react at a temperature of from 120 ℃ to 150 ℃ for 1 to 3 hours, and remove the xylene by vacuum extraction And (b) adding 200 to 900 parts by weight of a polyoxyethylene fatty acid ester to 100 to 300 parts by weight of the first polymer A obtained in (a). And reacting at a temperature of 120 ° C. to 150 ° C. for 4 to 10 hours to obtain the second polymer B, and (c) 100 to 100 of the second polymer B obtained in (b). 900 parts by weight of metal Material powder 100 parts by weight to 900 parts by weight were kneaded, to provide a step of producing a laser sintering shaping metal colloid composition, a manufacturing method of laser sintering shaping metal colloid containing.

  In the present invention, the method of “kneading” is not particularly limited, but any kneading method known in the prior art may be used as long as it does not depart from the spirit of the present invention. . As an example, for example, planetary mixer, paddle type mixer, high-speed extruder, high-speed polishing mixer, high-speed mill, high-speed stirrer, high-speed mixer, extruder, heating roller, kneader, roller mixer, Bamburi mixer, etc. The method of kneading | mixing (A) component, (B) component, or more components is mentioned. Further, from the viewpoint of productivity, it is preferable to perform kneading with a single screw extruder, a twin screw extruder, a kneader, a Banbury mixer, a high speed extruder, a high speed polishing mixer, a high speed mill or the like. .

  ADVANTAGE OF THE INVENTION According to this invention, the metal colloid used for laser sintering shaping | molding which consists of a metal material powder, a bisphenol A ethoxylate, xylene, and a polyoxyethylene fatty acid ester can be provided. First, the bisphenol A ethoxylate is reacted with the xylene to form the first polymer A, and then the first polymer A is further reacted with the polyoxyethylene fatty acid to form the second polymer B. Formed. Next, the metal colloid was formed by uniformly dispersing the metal material powder in the second polymer B. In the first polymer A, when the bisphenol A ethoxylate content is 500 to 2000 parts by weight, the xylene content is preferably 200 to 800 parts by weight. In the metal colloid for laser sintering modeling, the content of the metal material powder is preferably in the range of 100 to 900 parts by weight, and the content of the polymer B is preferably in the range of 900 to 100 parts by weight. .

  In the metal colloid for laser sintering modeling and the manufacturing method thereof according to the present invention, the first polymer A is a polymer including a monomer represented by the following chemical formula (A).

  In the metal colloid for laser sintering modeling and the manufacturing method thereof according to the present invention, the second polymer B is a polymer containing a monomer represented by the chemical formula (B).

  First, specific terms and nouns used in the present specification will be described. Unless otherwise specified, the following description is merely an exemplary description and limits the specification and claims of the present invention. It is not a thing. Unless defined otherwise, scientific and technical terms used herein have the same meaning as understood and used by one of ordinary skill in the art to which this invention belongs.

  In the present specification, numerical values and parameters for limiting the scope of the present invention generally include inevitable standard deviations resulting from individual test methods. Most of these numerical values and parameters are represented by approximate numerical values, but as far as possible, specific numerical values are accurately presented as related numerical values in the embodiments. In this specification, the range of the upper and lower limits of a numerical value to which “about” is added is usually determined by the thought of those skilled in the art to which the present invention pertains. However, in general, the actual numerical value is a numerical value including a standard error value that is acceptable for the average value. For example, when the predetermined numerical value is A, the actual numerical value is a numerical value that also includes upper and lower limit ranges such as A ± 10%, A ± 5%, A ± 1%, A ± 0.5%. It can be either.

Hereinafter, the present invention will be described in more detail with reference to examples.
According to one aspect of the present invention, a method for producing a metal colloid for laser sintering modeling,
(A) After reacting 500 to 2000 parts by weight of bisphenol A ethoxylate with 0.25 to 2 parts by weight of catalyst at a temperature of 140 to 180 ° C. for 4 to 8 hours, adding 200 to 800 parts by weight of xylene and adding 120 to 120 ° C. Obtaining a first polymer A by reacting at a temperature of ˜150 ° C. for 1 to 3 hours and then removing xylene by a vacuum extraction method;
(B) After adding 200 to 900 parts by weight of the polyoxyethylene fatty acid ester to 100 to 300 parts by weight of the first polymer A obtained in the step (a), at a temperature of 120 ° C to 150 ° C. Obtaining the second polymer B by reacting for 4 to 10 hours;
(C) 100-900 parts by weight of the second polymer B obtained in the step (b) and 100-900 parts by weight of the metal material powder are polished and kneaded at high speed for laser sintering modeling. Making a metal colloidal composition.

  In one specific example of the method for producing a metal colloid for laser sintering modeling of the present invention, before step (a), bisphenol A ethoxylate is previously added at a temperature of 200 ° C. to 260 ° C. 4. It further includes the step of heat-treating for ~ 8 hours.

  Next, in one specific embodiment according to the method for producing a metal colloid for laser sintering modeling of the present invention, the blending ratio of the bisphenol A ethoxylate and the catalyst in step (a) is not particularly limited. For example, when the said bisphenol A ethoxylate is 500-2000 weight part, it is preferable that the compounding quantity of the said catalyst is 0.25-2 weight part with respect to the said bisphenol A ethoxylate.

  In this step (a), the reaction temperature and reaction time when the prophenol ether and the catalyst are reacted are not particularly limited. For example, the reaction is performed at a temperature of 140 ° C. to 180 ° C. for 4 to 8 hours. It is preferable to make it.

  In this step (a), the amount of xylene added is not particularly limited. For example, when the bisphenol A ethoxylate is 500 to 2000 parts by weight, the xylene is added to the bisphenol A ethoxylate, It is preferable to add 200 to 800 parts by weight.

  In this step (a), the reaction temperature and reaction time when further reacting with xylene after the reaction of the bisphenol A ethoxylate and the catalyst are not particularly limited. For example, a temperature of 120 ° C. to 150 ° C. It is preferable to make it react for 1-3 hours.

Furthermore, in this step (a), the catalyst is not particularly limited.
In one specific embodiment of the metal colloid for laser sintering modeling of the present invention, the metal powder is not particularly limited. For example, a metal product can be formed by using 3D printing technology. Any one selected from other constituent materials may be used.

  Next, in one specific embodiment according to the method for producing a metal tape for laser sintering modeling of the present invention, the first polymer A includes a monomer represented by the following chemical formula (A). A polymer is preferred.

  In one specific embodiment of the method for producing a metal colloid for laser sintering modeling of the present invention, the second polymer B is a polymer containing a monomer represented by the chemical formula (B). It is preferable.

  As mentioned above, according to this invention, the metal colloid for laser sintering shaping | molding and its preparation method could be provided.

  In the following, the embodiments of the present invention will be described in more detail by giving various examples to make the spirit and contents of the present invention more complete and easy to understand. It should be understood that the invention is not limited to these embodiments, and that other equivalent or equivalent functions and procedures can be used to accomplish the invention.

  Further, the actual scope of the present invention can be further proved by the following specific examples, but these examples do not limit the scope of the present invention in any way.

(Production of metal colloid MP1)
First, 1000 g of bisphenol A ethoxylate (molecular weight: 200 to 600 g / mol) is put into a glass round bottle, heated to a temperature of about 200 ° C. to 260 ° C., held for 4 hours, and then about 0.5 g of catalyst is added. The mixture is cooled to about 140 ° C. to 180 ° C. and allowed to react for 6 hours. Subsequently, 400 g of xylene is added and the temperature is raised to 120 ° C. to 150 ° C. After completion of the reaction, xylene was removed by a vacuum extraction method to obtain a polymer A1 containing a monomer represented by the following chemical formula (A).

  Subsequently, 900 g of polyoxyethylene fatty acid ester is added to 100 g of the polymer A1 obtained above, and the mixture is reacted at a temperature of 120 ° C. to 150 ° C. for 4 to 10 hours. The monomer represented by the following chemical formula (B) A polymer B1 containing was produced.

900 g of the polymer B1 and 100 g of iron metal powder were mixed with a high-speed mill for 4 to 8 hours to prepare a metal colloid MP1 for laser sintering modeling.
Subsequently, when the metal colloid MP1 obtained as described above is used to repair a damaged metal part during 3D printing, the metal colloid MP1 can be easily placed on the vertical cross section of the damaged metal part. Can be completed successfully. Therefore, by using the metal colloid MP1 provided by the present invention, the working time and cost can be shortened without disassembling or updating the parts, and the precision of the damaged or defective metal parts or defective metal products can be reduced. Repair is possible.

(Production of metal colloid MP2)
First, 1500 g of bisphenol A ethoxylate (molecular weight: 200 to 600 g / mol) is put into a glass round bottle, heated to a temperature of about 200 ° C. to 260 ° C., held for 4 hours, and then about 0.75 g of catalyst is added. The mixture is cooled to a temperature of about 140 ° C. to 180 ° C. and allowed to react for 6 hours. Subsequently, 600 g of xylene is added, and the temperature is raised to 120 ° C. to 150 ° C. and reacted for 1 to 3 hours. After completion of the reaction, xylene was removed by a vacuum extraction method to obtain a polymer A2 containing a monomer represented by the following chemical formula (A).

  Subsequently, 800 g of polyoxyethylene fatty acid ester is added to 200 g of the polymer A2 obtained above and reacted at a temperature of 120 ° C. to 150 ° C. for 4 to 10 hours. A monomer represented by the following chemical formula (B) A high molecular polymer B2 was prepared.

800 g of the polymer B2 and 200 g of the aluminum metal powder were mixed with a high-speed mill for 4 to 8 hours to produce a laser colloidal metal colloid MP2.
Subsequently, when the metal colloid MP2 obtained as described above is used to repair a damaged metal part during 3D printing, the metal colloid MP2 can be easily placed on the vertical cross section of the damaged metal part. Can be completed successfully. Therefore, by using the metal colloid MP2 provided by the present invention, the working time and cost can be shortened without disassembling or renewing the parts, and the precision of the damaged or defective metal parts or defective metal products can be reduced. Repair is possible.

(Production of metal colloid MP3)
First, 2,000 g of bisphenol A ethoxylate (molecular weight: 200 to 600 g / mol) is put into a glass round bottle, heated to a temperature of about 200 ° C. to 260 ° C., held for 4 hours, and then about 2.0 g of catalyst is added. And cooled to a temperature of about 140 ° C. to 180 ° C. and allowed to react for 6 hours, followed by adding 800 g of xylene and raising the temperature to 120 ° C. to 150 ° C. and reacting for 1 to 3 hours. After completion of the reaction, xylene was removed by a vacuum extraction method to obtain a polymer A3 containing a monomer represented by the following chemical formula (A).

  Subsequently, 700 g of polyoxyethylene fatty acid ester is added to 300 g of the polymer A1 obtained above, and reacted at a temperature of 120 ° C. to 150 ° C. for 4 to 10 hours. A monomer represented by the following chemical formula (B) is obtained. A high molecular polymer B3 was prepared.

900 g of the polymer B3 and 100 g of nickel metal powder were mixed in a high speed mill for 4 to 8 hours to prepare a metal colloid MP3 for laser sintering modeling.
Subsequently, when the metal colloid MP3 obtained as described above is used to repair a damaged metal part during 3D printing, the metal colloid MP3 can be easily placed on the vertical cross section of the damaged metal part. Can be completed successfully. Therefore, by using the metal colloid MP3 provided by the present invention, the working time and cost can be reduced without disassembling or updating the parts, and the precision of the damaged or defective metal parts or defective metal products can be reduced. Repair is possible.

  As is apparent from the above description, the present invention provides a metal colloid for laser sintering modeling in which a metal material powder is uniformly dispersed in a polymer polymer comprising bisphenol A ethoxylate, xylene, and polyoxyethylene fatty acid ester. And the method of producing this metal colloid for laser sintering modeling can be provided. According to the metal colloid for laser sintering modeling provided by the present invention, it is possible to directly lay the metal colloid on the part to be repaired of the metal workpiece in the 3D printing process, and the problem of blowing off the powder in the traditional 3D process. This eliminates the need to install an additional powder recovery system, reduce the use and waste of metal powder, and reduce processing costs.

  Next, by using the metal colloid for laser sintering modeling provided by the present invention, it is possible to repair metal parts with a three-dimensional structure without disassembling or renewing the parts. It is possible to achieve an excellent effect such that precise repair of a defective metal part or defective metal product becomes possible.

  According to the present invention, when performing laser sintering, the metal powder is carried to the positioning point at the time of laser sintering by the colloidal viscosity so as not to be affected by different geometric characteristics of the parts. Furthermore, 3D printing can repair a workpiece with two or more types of alloy metal materials, and can obtain a more suitable structural strength when sintering the original material and the powder in the colloid.

  In addition, the metal colloid of the present invention complements the change in the ratio due to the sintering of the alloy powder, restores the stability of the metal strength, and moves the spindle to the repair site by accurately moving the spindle with a three-axis machine. If laid directly, it can be repaired smoothly in any geometric space.

  As described above, the contents of the present invention are exemplified by the above-described embodiments, but the present invention is not limited to these embodiments. Those skilled in the art to which the present invention pertains can make various modifications and improvements without departing from the spirit of the present invention. For example, the technical contents exemplified in the above embodiments may be combined, or new embodiments may be combined. Modifications and these embodiments are also considered to belong to the present invention. Accordingly, the scope protected in this case includes the claims and the defined scope thereof as described below.

Claims (6)

A method for producing a metal colloid for laser sintering modeling,
(A) forming a first polymer A by reacting 500 to 2000 parts by weight of bisphenol A ethoxylate (BPA-EO) with 200 to 800 parts by weight of xylene under the first reaction conditions;
(B) 100 to 300 parts by weight of the first polymer A obtained in (a) and 200 to 900 parts by weight of a polyoxyethylene fatty acid ester are reacted under the second reaction condition to obtain a second Forming a polymer B of
(C) forming a metal colloid by kneading the second polymer B obtained in (b) above into a metal material powder;
In a method for producing a metal colloid for laser sintering modeling including:
The first reaction condition in the step (a) is that the catalyst is added to bisphenol A ethoxylate for 4 to 8 hours at a temperature of 140 ° C. to 180 ° C., then xylene is added, and 120 ° C. to 150 ° C. Reaction for 1 to 3 hours at a temperature of
The second reaction condition in the step (b) is to react at a temperature of 140 ° C. to 180 ° C. for 1 to 3 hours,
The method for producing a metal colloid for laser sintering modeling, wherein a weight ratio between the second polymer B and the metal material powder in the step (c) is 1: 9 to 9: 1. The method for producing a metal colloid for laser sintering modeling according to claim 1, wherein the first polymer A is a polymer containing a monomer represented by the following chemical formula (A).
The method for producing a metal colloid for laser sintering modeling according to claim 1 or 2, wherein the second polymer B is a polymer containing a monomer represented by the chemical formula (B).
The method for producing a metal colloid for laser sintering modeling according to any one of claims 1 to 3, wherein the addition amount of the catalyst is 0.25 to 2 parts by weight. 5. The heat treatment of bisphenol A ethoxylate at a temperature of 200 ° C. to 260 ° C. for 4 to 8 hours before the step (a) is further included. The manufacturing method of the metal colloid for laser sintering shaping | molding of description. At least a metal colloid for laser sintering modeling comprising a metal material powder, bisphenol A ethoxylate, xylene, and polyoxyethylene fatty acid ester,
The metal colloid for laser sintering modeling forms the first polymer A by first reacting the bisphenol A ethoxylate with the xylene by the production method according to any one of claims 1 to 5. Then, after forming the second polymer B by reacting the first polymer A with the polyoxyethylene fatty acid ester, the metal material powder is further uniformly dispersed in the second polymer B. Obtained,
In the first polymer A, the bisphenol A ethoxylate content is 500 to 2000 parts by weight, and the xylene content is 200 to 800 parts by weight.
In the laser colloid for laser sintering modeling, the content of the metal material powder is 100 to 900 parts by weight, and the content of the second polymer B is 900 to 100 parts by weight. Metal colloid for sintering modeling.