WO2019075869A1

WO2019075869A1 - 3d-printing molded wax having high rigidness and toughness balance and preparation method therefor

Info

Publication number: WO2019075869A1
Application number: PCT/CN2017/114123
Authority: WO
Inventors: 张金汉; 陈樟
Original assignee: 惠州市优恒科三维材料有限公司
Priority date: 2017-10-19
Filing date: 2017-11-30
Publication date: 2019-04-25
Also published as: CN107936582A; CN107936582B

Abstract

A 3D-printing molded wax having high rigidness and toughness balance comprises the following components by weight: 10 to 50 Kg of hard wax, 0 to 50 Kg of soft wax, 5 to 30 Kg of tackifier, 0.1 to 1 Kg of nucleating agent, 1 to 20 Kg of a filler, 0.5 to 1 Kg of surfactant, 0.5 to 1 Kg of dispersant, 0.1 to 0.5 Kg of antioxidant and 0 to 1 Kg of a toner. A preparation method for the molded wax. The rigidity and toughness of the 3D-printing molded wax are regulated by means of the hard wax and the soft wax; by adding the nucleating agent, the crystallization of the wax is promoted and wax crystals are refined, so that the cooling speed of the 3D printing molded wax is fast, the surface finish of the 3D-printing molded wax is high, and the rigidness and toughness balance of the material is improved; the monodisperse polystyrene microspheres can stably disperse and exist in the wax by means of the surfactant and the dispersing agent, and sedimentation is prevented, and accordingly, a spraying head is prevented from being blocked. The components in the 3D-printing molded wax easily volatilize at a casting temperature, and the MJP 3D printing fineness is high, and accordingly, the fineness of cast metal products is high.

Description

High toughness and tough balance 3D printing molding wax and preparation method thereof

Technical field

The invention relates to the field of preparation of 3D printing materials, in particular to a high toughness balanced 3D printing molding wax and a preparation method thereof.

Background technique

Compared with traditional technology, 3D printing wax mold has the advantages of cost saving, high intelligence, high complexity and no need for mold. Therefore, the lost foam casting process can be widely used in precision casting industry such as jewelry. At present, 3D printing wax is divided into wire, powder and block, 3D printing wax for FDM (melt deposition type) 3D printer, 3D printing wax for SLS (selective laser sintering) 3D printer, 3D printing wax The block is used for MJP (multi-headjet) 3D printer, in which the MJP 3D printer can print at a precision of 16μm and has a fast printing speed, which has the advantages that FDM and SLS 3D can't match, so it has great application prospects. Chinese patent CN106317913A uses 3D printing wax line prepared by industrial casting wax, polyolefin resin, polyethylene wax and stearic acid. The polyolefin resin is difficult to volatilize and the lost foam casting performance of printing wax is not good, and the material is used for FDM 3D. Printing causes poor printing accuracy. Chinese patent CN104693579B uses a wax powder, stearic acid or stearate, white carbon black, carbon black and chopped carbon fiber to prepare printing wax powder, but this material is used for SLS 3D printing, resulting in poor printing accuracy, white carbon black, The presence of carbon black and chopped carbon fibers is also detrimental to lost foam casting. Chinese patent CN105504836A uses paraffin, viscosity modifier, antioxidant, tough polymer, plasticizer, high hardness polymer, low shrinkage resin, inorganic filler, dye, phase transfer agent to prepare low penetration wax for 3D printing. Used in MJP 3D printers, but tough polymers, high hardness polymers, low shrinkage resins and inorganic fillers are difficult to volatilize at high temperatures and are difficult to apply to lost foam casting. World Patent WO2010132392A2 uses a hydrocarbon wax mixed with a hydrocarbon resin to obtain a 3D printing wax for use in an MJP 3D printer, but the molding wax has problems such as being brittle, brittle, poor in oxidation resistance, and incapable of recycling.

Summary of the invention

The object of the present invention is to overcome the deficiencies of the prior art, and to provide a high toughness and tough balance 3D printing molding wax and a preparation method thereof. The high toughness and tough balance 3D printing molding wax of the invention has good toughness, is not brittle, has good rigidity, and loses wax performance. Good, high printing accuracy, good oxidation resistance, and recyclability.

In order to achieve the above object, the present invention provides a high toughness balanced 3D printing molding wax, the material comprising The composition of the weight Kg number:

Preferably, the hard wax is paraffin wax, microcrystalline wax, polyethylene wax, polypropylene wax, polyamide wax, synthetic wax, beeswax, insect wax, cetyl wax, hair wax, shellac wax, palm wax, fruit At least one of wax, ash wax, soybean wax, rice bran wax, sugar cane wax, bay wax, ramie wax, wood wax, lacquer wax, palm wax, and pine wax, wherein the melting temperature of the hard wax is 65 ° C - 85 °C, penetration ≤ 12 1/10mm (25 ° C, 100g). The hard wax imparts rigidity to the 3D printing wax.

Preferably, the soft wax is paraffin wax, microcrystalline wax, polyethylene wax, polypropylene wax, polyamide wax, synthetic wax, beeswax, insect wax, cetyl wax, hair wax, shellac wax, palm wax, fruit At least one of wax, ash wax, soybean wax, rice bran wax, sugar cane wax, bay wax, ramie wax, wood wax, lacquer wax, palm wax, and pine wax, wherein the soft wax has a melting temperature of 65 ° C - 85 °C, penetration >12 1/10mm (25°C, 100g). The soft wax imparts toughness to the 3D printed wax.

Preferably, the tackifier is at least one of a hydrogenated hydrocarbon resin, an alicyclic hydrocarbon resin, and a hydrogenated rosin ester, wherein the tackifier softening temperature is from 90 ° C to 150 ° C. The tackifier is used to adjust the viscosity of the 3D printing wax to meet the adhesion between the layers when printing, and to prevent the printing sheet from being molded due to insufficient adhesion.

Preferably, the nucleating agent is stearate, sorbitol, benzoate, succinate, glutarate, hexanoate, adipic acid, adipate, benzoate, At least one of cinnamate and β-naphthoate. The nucleating agent can promote the crystallization of the wax and refine the wax crystal, which not only makes the 3D printing wax have a fast cooling speed, a high surface smoothness, but also improves the rigidity and toughness balance of the material. In addition, the nucleating agent is easily volatilized and does not affect the effect of lost foam casting.

Preferably, the filler is a monodisperse polystyrene microsphere, wherein the monodisperse polystyrene microspheres have a particle diameter of from 5 nm to 500 nm.

Polystyrene can be completely decomposed into styrene gas at around 450 ° C, so it is suitable for use as a material for lost foam casting. At present, polystyrene and wax are the two most common materials for lost foam casting. Polystyrene is introduced into the 3D printing molding wax, and its rigidity not only imparts rigidity to the 3D printing molding wax, but its size effect enables nano-toughening of the 3D printing molding wax.

Preferably, the surfactant is at least one of a sulfonate, an alkyl alcohol amide, a polyoxyethylene ether, and a guar gum. Kind. The surfactant can make the monodisperse polystyrene microspheres stably exist in the wax, prevent the sedimentation thereof, thereby preventing the clogging of the nozzle, and the surfactant is easy to be thermally volatilized, and does not affect the effect of the lost foam casting.

Preferably, the dispersing agent is at least one of a polyurethane copolymer, a block type polymer, a polyvalent carboxylic acid polymer, a polyamide amide polycarboxylate, an alkylamine salt polymer, and a polycarboxylic acid polyester. The dispersing agent enables the monodisperse polystyrene microspheres to be stably dispersed in the wax to prevent sedimentation thereof, thereby preventing clogging of the nozzle, and the dispersing agent is easily thermally volatilized, and does not affect the effect of lost foam casting.

Preferably, the antioxidant is at least one of a hindered phenol, a hindered amine, a phosphite, and a sulfate, wherein the complete thermal decomposition temperature of the antioxidant is ≤450 °C. The antioxidant can impart excellent oxidation resistance to the 3D printing wax, which is difficult to deteriorate during processing, and can be repeatedly recycled and reused.

The preparation method of the above high-rigidity balanced 3D printing molding wax comprises the following steps:

Step 1: According to the group distribution ratio, the raw materials of each component are weighed, and the components are mechanically mixed uniformly;

Step 2: heating and melting the uniformly mixed raw materials at 70 ° C to 200 ° C while continuously stirring to obtain a uniform dispersion;

Step 3: The uniform dispersion is filtered at a constant temperature of 60 ° C to 120 ° C to obtain a finished product, wherein the filter paper has a pore size of 1 μm to 5 μm.

Compared with the prior art, the present invention has the following beneficial effects:

1 using hard wax and soft wax to adjust the rigidity and toughness of 3D printing wax;

2 By adding a nucleating agent, the wax can be crystallized and the wax crystal can be refined, which not only makes the 3D printing wax have a fast cooling speed, high surface smoothness, but also improves the rigidity and toughness balance of the material;

3 polystyrene can be completely decomposed into styrene gas at about 450 °C, and the introduction of nano-sized monodisperse polystyrene microspheres into 3D printing molding wax will not only impart rigidity to 3D printing wax, but also nano toughen. 3D printing molding wax;

4 Surfactants and dispersants can stably disperse and exist monodisperse polystyrene microspheres in the wax to prevent sedimentation, thereby preventing clogging of the nozzle;

The components in the 53D printing wax are easily volatilized at the casting temperature, and the fineness of the MJP 3D printing is high, so the metal parts of the casting are fine.

Detailed ways

The weight Kg hereinafter may represent a unit amount conventionally used in the art, such as kilograms, grams, etc., and may also mean a ratio between components, such as mass or weight ratio.

The high toughness-balanced 3D printing molding wax of the present invention will be described in detail below in conjunction with specific preferred embodiments.

Example 1:

Step S11: 50Kg of palm wax, 10Kg of microcrystalline wax, 5Kg of rosin ester, 0.1Kg of sodium stearate, 1Kg of monodisperse polystyrene microspheres with particle diameter of 5nm, 0.5Kg of guar gum, 0.5Kg of polyurethane copolymer , the hindered phenolic antioxidant 0.1Kg, 1 part of the toner is weighed the raw materials of each component, and the components are mechanically mixed uniformly;

Step S12: heating and melting the uniformly mixed raw materials at 70 ° C while continuously stirring to obtain a uniform dispersion;

Step S13: The uniform dispersion was filtered at a constant temperature at 60 ° C to obtain a finished product, wherein the filter paper had a pore size of 1 μm.

Example 2:

Step S21: 50 kg of synthetic wax, 50 kg of beeswax, 30 kg of alicyclic hydrocarbon resin, 1 kg of sorbitol, 20 kg of monodisperse polystyrene microspheres having a particle diameter of 500 nm, 1 kg of alkyl alcohol amide, 1 kg of block type polymer, hindered amine 0.5Kg of antioxidants are weighed into the raw materials of each component, and the components are mechanically mixed uniformly;

Step S22: heating and melting the uniformly mixed raw materials at 200 ° C while continuously stirring to obtain a uniform dispersion;

Step S23: The uniform dispersion was filtered at a constant temperature at 120 ° C to obtain a finished product, wherein the filter paper had a pore size of 5 μm.

Example 3:

Step S31: 50Kg of paraffin wax, 20Kg of microcrystalline wax, 20Kg of hydrogenated petroleum resin, 0.2Kg of benzoate, 10Kg of monodisperse polystyrene microspheres with a particle diameter of 20 nm, 0.5 Kg of sulfonate, 0.5 polycarboxylic acid polymer Kg, phosphite antioxidant 0.2Kg is weighed the raw materials of each component, and the components are mechanically mixed uniformly;

Step S32: heating and melting the uniformly mixed raw materials at 150 ° C while continuously stirring to obtain a uniform dispersion;

Step S33: The uniform dispersion was filtered at a constant temperature at 80 ° C to obtain a finished product, wherein the filter paper had a pore size of 2 μm.

Example 4:

Step S41: 40Kg of paraffin wax, 20Kg of beeswax, 20Kg of hydrogenated petroleum resin, 0.3Kg of sodium hexate, 20Kg of monodisperse polystyrene microspheres with particle diameter of 50nm, 0.3Kg of ethoxylated vinyl ether, 0.3Kg of polycarboxylic acid polyester The sulfate-based antioxidant 0.3Kg is weighed into the raw materials of each component, and the components are mechanically mixed uniformly;

Step S42: heating and melting the uniformly mixed raw materials at 120 ° C while continuously stirring to obtain a uniform dispersion;

Step S43: The uniform dispersion was filtered at a constant temperature at 90 ° C to obtain a finished product, wherein the filter paper had a pore size of 1 μm.

Example 5:

Step S51: according to polyethylene wax 45Kg, synthetic wax 15Kg, hydrogenated petroleum resin 25Kg, sodium cinnamate 0.2Kg, particle size 80nm monodisperse polystyrene microspheres 15Kg, alkyl alcohol amide 0.2Kg, alkylamine salt polymerization 0.2Kg, The hindered phenolic antioxidant 0.2Kg is weighed into the raw materials of each component, and the components are mechanically mixed uniformly;

Step S52: heating and melting the uniformly mixed raw materials at 140 ° C while continuously stirring to obtain a uniform dispersion;

Step S53: The uniform dispersion was filtered at a constant temperature at 85 ° C to obtain a finished product, wherein the filter paper had a pore size of 3 μm.

Example 6

Step S61: according to paraffin wax 45Kg, microcrystalline wax 25Kg, hydrogenated petroleum resin 15Kg, sodium stearate 0.4Kg, monodisperse polystyrene microspheres with a particle size of 10nm 15Kg, sulfonate 0.4Kg, polyamide polycarboxylate 0.4Kg, 0.4Kg of hindered phenolic antioxidant, weigh each component raw material, and mechanically mix each component;

Step S62: heating and melting the uniformly mixed raw materials at 160 ° C while continuously stirring to obtain a uniform dispersion;

Step S63: The uniform dispersion was filtered at a constant temperature at 100 ° C to obtain a finished product, wherein the filter paper had a pore size of 2 μm.

Comparative example 1:

In Example 3, the hard wax was removed.

Comparative example 2:

In Example 3, the soft wax was removed.

Comparative example 3:

In Example 3, the polystyrene was removed.

Comparative example 4:

In Example 3, the surfactant was removed.

Comparative example 5:

In Example 3, the dispersant was removed.

Comparative example 6:

In Example 3, the antioxidant was removed.

Related performance tests:

The processing characteristics and product properties provided in the above Examples 1-6 and Comparative Examples 1-6 are shown in Table 1.

Table 1 Example and Comparative Processing Characteristics and Product Performance

It can be seen from the above comparison results that the present invention has good effects by adjusting the rigidity and toughness of the 3D printing wax by using hard wax and soft wax; and at the same time, the crystallization and refinement of the wax can be promoted by adding a nucleating agent. The wax crystal not only makes the 3D printing wax print faster in cooling speed and surface smoothness, but also improves the toughness balance of the material; polystyrene can be completely decomposed into styrene gas at 450 °C, and the nano-particle size is monodispersed. The introduction of styrene microspheres into 3D printing wax not only imparts rigidity to 3D printing wax, but also nano-toughened 3D printing wax; surfactants and dispersing agents can make monodisperse polystyrene microspheres in wax Stable dispersion and presence prevent sedimentation and prevent clogging of the nozzle; the components in the 3D printing wax are easily volatilized at the casting temperature, and the fineness of the MJP 3D printing is high, so the fineness of the cast metal parts is high. .

The above is a detailed description of a 3D printing molding wax and a preparation method thereof provided by the embodiments of the present invention. The principles and embodiments of the present invention have been described with reference to the specific embodiments thereof. The description of the embodiments is only for the purpose of understanding the method of the present invention and the core idea thereof, and the above description is only the preferred embodiment of the present invention. The invention is not intended to limit the invention, and any modifications, equivalents and improvements made within the spirit and scope of the invention are intended to be included within the scope of the invention.

Claims

A high toughness balanced 3D printing molding wax characterized by comprising the following components:
The high toughness-balanced 3D printing molding wax according to claim 1, wherein the hard wax is paraffin wax, microcrystalline wax, polyethylene wax, polypropylene wax, polyamide wax, synthetic wax, beeswax, Insect wax, cetyl wax, hair wax, shellac wax, palm wax, fruit wax, tree wax, soybean wax, rice bran wax, sugar cane wax, bay wax, castor wax, wood wax, paint wax, palm wax, pine wax At least one of the hard waxes has a melting temperature of from 65 ° C to 85 ° C and a penetration of ≤ 12 1/10 mm (25 ° C, 100 g).
The high toughness-balanced 3D printing molding wax according to claim 1, wherein the soft wax is paraffin wax, microcrystalline wax, polyethylene wax, polypropylene wax, polyamide wax, synthetic wax, beeswax, Insect wax, cetyl wax, hair wax, shellac wax, palm wax, fruit wax, tree wax, soybean wax, rice bran wax, sugar cane wax, bay wax, castor wax, wood wax, paint wax, palm wax, pine wax At least one of the soft waxes has a melting temperature of from 65 ° C to 85 ° C and a penetration of > 12 1/10 mm (25 ° C, 100 g).
The high toughness-balanced 3D printing molding wax according to claim 1, wherein the tackifier is at least one of a hydrogenated hydrocarbon resin, an alicyclic hydrocarbon resin, and a hydrogenated rosin ester. The softening temperature of the adhesive is from 90 ° C to 150 ° C.
The high toughness-balanced 3D printing molding wax according to claim 1, wherein the nucleating agent is stearate, sorbitol, benzoate, succinate, glutarate, and At least one of a salt, adipic acid, adipate, benzoate, cinnamate, and β-naphthoate.
The high toughness-balanced 3D printing molding wax according to claim 1, wherein the filler is monodisperse polystyrene microspheres, wherein the monodisperse polystyrene microspheres have a particle diameter of 5 nm to 500 nm. .
A high toughness-balanced 3D printing molding wax according to claim 1, wherein said surfactant It is at least one of a sulfonate, an alkyl alcohol amide, a polyoxyethylene ether, and a guar gum.
The high toughness-balanced 3D printing molding wax according to claim 1, wherein the antioxidant is at least one of a hindered phenol, a hindered amine, a phosphite, and a sulfate. The complete thermal decomposition temperature of the antioxidant is ≤ 450 °C.
A high toughness-balanced 3D printing molding wax according to claim 1, wherein the dispersing agent is a polyurethane copolymer, a block type polymer, a polycarboxylic acid polymer, a polyamide polycarboxylate, or an alkane. At least one of a base amine salt polymer and a polycarboxylic acid polyester.
A method for preparing a high toughness-balanced 3D printing molding wax according to any one of claims 1 to 9, comprising the steps of:

(1) According to the group distribution ratio, the raw materials of each component are weighed, and the components are mechanically mixed uniformly;

(2) heating and melting the uniformly mixed raw materials at 70 ° C to 200 ° C while continuously stirring to obtain a uniform dispersion;

(3) The uniform dispersion is filtered at a constant temperature of 60 ° C to 120 ° C to obtain a finished product, wherein the filter paper has a pore size of from 1 μm to 5 μm.