WO2019085134A1

WO2019085134A1 - 3d printing wax that is crosslinkable, contributes to fast printing speed and high printing precision and can be used for both casting and model printing, and manufacturing method thereof

Info

Publication number: WO2019085134A1
Application number: PCT/CN2017/114128
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: 2017-10-30
Filing date: 2017-11-30
Publication date: 2019-05-09
Also published as: CN107915898B; CN107915898A

Abstract

Provided is a 3D printing wax that is crosslinkable, contributes to fast printing speed and high printing precision, and can be used for both casting and model printing. The wax comprises the following parts by weight: 20-90 parts of an unsaturated wax, 5-30 parts of a tackifier, 0.1-1 parts of a nucleating agent, 0.1-1 parts of a compatibilizer, 1-20 parts of a photosensitive resin, 0.5-1 parts of a photoinitiator, 0.5-1 parts of a crosslinking agent, 0.1-0.5 parts of an antioxidant, and 0-1 parts of a toner. The 3D printing wax is characterized by good lost-wax casting performance, contributes to fast printing speed and high printing precision, and is crosslinkable. It also has the advantages of good toughness, strength, and rigidity once crosslinked. The 3D printing wax can be applied to both fields of lost-wax casting and model printing.

Description

3D printing forming wax which can be cross-linked, fast printing speed, high printing fineness, can be used for casting and model at the same time and preparation method thereof

Technical field

The invention relates to the field of preparation of 3D printing materials, in particular to a 3D printing molding wax which can be crosslinked, has a fast printing speed, has high printing precision, can be used for casting and model at the same time, 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. 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 and brittle. In order to improve the toughness of the molding wax, Chinese patent CN106118082A is 30-50% paraffin wax, 2-5% beeswax, 5-10% epoxy resin, 2-3% curing agent, 2-20% viscosity modifier, toughening polymer. 3D printing wax is prepared by 20-30%, high hardness polymer 6-25%, filler 2-4%, dye 0.1-0.3%, phase transfer agent 2-4%, but the material has the following disadvantages: 1 toughening Polymer, high hardness polymer, filler, phase transfer agent are all difficult to decompose or volatilize materials. 3D printed wax mold is not suitable for lost foam casting, only suitable for use as appearance parts; 2 paraffin wax as main wax for forming wax, heat dissipation Slow, fast printing speed will result in inability to heat up in time and cannot be accurately formed and cracked. 3 The material has large crystals, poor crystallinity, and poor compatibility between components, resulting in a rough surface after 3D printing.

Summary of the invention

The object of the present invention is to overcome the deficiencies of the prior art, and to provide a 3D printing molding wax which can be crosslinked, has a fast printing speed, is high in printing fineness, can be simultaneously used for casting and modeling, and a preparation method thereof, 3D of the present invention. The printing wax has the characteristics of good wax loss, fast printing, high printing precision and cross-linking. It has the advantages of good toughness, high strength and good rigidity after cross-linking, and can be applied to both lost wax casting and printing models. Fields.

In order to achieve the above object, the present invention provides a 3D printing molding wax which is crosslinkable, fast in printing speed, high in print fineness, and can be used for both casting and molding, and includes the following parts by weight:

Preferably, the unsaturated wax is at least one of a polyethylene wax and a polypropylene wax, wherein the unsaturated wax has a melting temperature of 65 ° C to 120 ° C. Unsaturated wax has good heat dissipation performance, can meet the requirements of fast printing, has unsaturated bonds, can be cross-linked, and has greatly improved mechanical properties after cross-linking.

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, high printing precision, 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 compatibilizing agent is a cyclic anhydride type compatibilizer based on an unsaturated wax, a carboxylic acid type compatibilizer, an epoxy type compatibilizer, an imide type compatibilizer, and an isocyanate type. At least one of the compatibilizers. Compatibilizers are used to improve the compatibility between the unsaturated wax and the photosensitive resin, thereby improving the properties of the material.

Preferably, the photosensitive resin is at least one of urethane acrylate, epoxy acrylate, polyether acrylate, polyester polypropionate, and polyethylene glycol dimethacrylate. After the wax mold is printed, it can be directly used for lost foam casting. The photosensitive resin does not affect the wax loss performance. When used for non-casting, the wax mold is treated under ultraviolet light, and the photosensitive resin contained in the ultraviolet light will be irradiated. Curing occurs to improve mechanical properties.

Preferably, the photoinitiator is 2,4,6 (trimethylbenzoyl)diphenylphosphine oxide, ethyl 2,4,6-trimethylbenzoylphosphonate, 2-methyl 1-[4-methylthiophenyl]-2-morpholinyl-1-propanone, 2-isopropylthioxanthone (2,4 isomer mixture, 1-hydroxy-cyclohexyl-phenyl) Ketone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, benzoin dimethyl ether, o-benzoylbenzene Methyl formate, benzophenone, 4-chlorobenzophenone, 4-phenylbenzophenone, 2-phenylbenzyl-2-dimethylamine-1-(4-morpholiniumbenzyl) Butanone, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, benzoylformate mixture, 2-hydroxy-1-(4-(2-hydroxy-2-methylpropanoyl) At least one of phenyl)benzyl)-2-methyl-1-propanone, bis 2,6-difluoro-3pyrrolephenyltitanocene, and 4-dimethylamino-benzoic acid ethyl ester. The photoinitiator photocures the photosensitive resin to improve the mechanical properties of the material.

Preferably, the crosslinking agent is at least one of an organic peroxide, an acid anhydride, and a vinyl triethoxysilane. After the wax mold is printed, it can be directly used for lost foam casting. The cross-linking agent does not affect the wax loss performance. When used in the model, the cross-linking agent can crosslink the unsaturated wax and form a bulk structure from the linear structure. Thereby improving the mechanical properties of the material.

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 invention also provides a method for preparing a 3D printing molding wax which can be cross-linked, has a fast printing speed, has high printing precision, can be used for casting and a model at the same time, and 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 - 120 ° C to obtain a finished product, wherein the filter paper has a pore size of 0.1 μm to 5 μm;

Step 4: Printing and molding by MJP 3D printer;

Step 5: Direct wax loss casting, or cross-linking curing, to obtain a wax mold with excellent mechanical properties, used to make a model.

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

(1) The invention adopts polyethylene wax and polypropylene wax as main wax, has rapid cooling, can satisfy fast printing, nucleating agent can promote wax crystallization and refine wax crystal, and not only cool the printing speed of 3D printing wax. Fast, high print quality, and improved material toughness balance;

(2) The invention introduces a photosensitive resin and a photoinitiator. After the wax mold is printed, it can be directly used for lost foam casting, and the photosensitive resin does not affect the loss of wax property, and when used for model non-casting, the wax mold is exposed to ultraviolet rays. Under the treatment, the photosensitive resin contained will be cured under ultraviolet irradiation to improve the mechanical properties;

(3) The present invention introduces a compatibilizing agent, which improves the compatibility between the components, thereby facilitating the improvement of the overall performance;

(4) The invention introduces a crosslinking agent, and after the wax mold is printed, it can be directly used for lost foam casting, and the crosslinking agent does not affect the lost wax property, and when used in the model, the crosslinking agent can make the unsaturated wax Cross-linking occurs, and a linear structure is used to generate a body structure, thereby improving the mechanical properties of the material.

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 3D printing molding wax of the present invention which can be crosslinked, has a fast printing speed, has high printing fineness, can be simultaneously used for casting and modeling, and a preparation method thereof will be described in detail below with reference to specific preferred embodiments.

Example 1:

Step S11: 90Kg of polypropylene wax, 5Kg of alicyclic hydrocarbon resin, 1Kg of stearate, 0.1Kg of carboxylic acid type compatibilizer, 1Kg of polyether acrylate, 0.5Kg of benzophenone, 0.5Kg of anhydride, hindered phenol Antioxidant 0.1Kg, 1 part of toner, weigh each component raw materials, and mechanically mix each component;

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 0.1 μm.

Step S14: MJP 3D printing molding.

Step S15: directly losing wax casting, or after cross-linking and solidifying, obtaining a wax mold excellent in mechanical properties for use in making a model.

Example 2:

Step S21: 20Kg of polyethylene wax, 30Kg of hydrogenated rosin ester, 0.1Kg of sorbitol, 1Kg of a cyclic anhydride type compatibilizer compatibilizer, 20Kg of polyester acrylate, 1Kg of benzoin dimethyl ether, 1Kg of organic peroxide, Phosphate antioxidant 0.5Kg is weighed into each component raw material, 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.

Step S24: MJP 3D printing molding.

Step S25: directly losing wax casting, or after cross-linking and solidifying, obtaining a wax mold excellent in mechanical properties for use in making a model.

Example 3:

Step S31: 80Kg of polyethylene wax, 20Kg of hydrogenated petroleum resin, 0.2Kg of benzoate, 0.3Kg of maleic anhydride grafted polyethylene wax, 10Kg of epoxy acrylate, 2,4,6 (trimethylbenzoyl group) ) 0.5Kg of diphenylphosphine oxide, 0.5Kg of organic peroxide, 0.2Kg of phosphite antioxidant, weighing the raw materials of each component, and mechanically mixing the components;

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.

Step S34: MJP 3D printing molding.

Step S35: directly losing wax casting, or after cross-linking and solidifying, obtaining a wax mold excellent in mechanical properties for use in making a model.

Example 4:

Step S41: 75Kg of polypropylene wax, 25Kg of hydrogenated petroleum resin, 0.3Kg of succinate, 0.5Kg of isocyanate grafted polyethylene wax, 8Kg of urethane acrylate, 0.5Kg of 4-dimethylamino-benzoic acid ethyl ester, vinyl three 0.8Kg of ethoxysilane, 0.2Kg of phosphite antioxidant, weigh each component, and mechanically mix the components;

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.

Step S44: MJP 3D printing molding.

Step S45: directly losing wax casting, or after cross-linking and solidifying, obtaining a wax mold excellent in mechanical properties for use in making a model.

Example 5:

Step S51: 80Kg of polyethylene wax, 20Kg of hydrogenated petroleum resin, 0.2Kg of benzoate, 0.3Kg of epoxy type compatibilizer, 12Kg of epoxy acrylate, bis 2,6-difluoro-3pyrrolyl phenyl Titanium 0.1Kg, TPO 0.3Kg, organic peroxide 0.6Kg, phosphite antioxidant 0.3Kg, weigh each component raw materials, and mechanically mix the components;

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.

Step S44: MJP 3D printing molding.

Example 6

Step S61: 80Kg of polyethylene wax, 20Kg of hydrogenated petroleum resin, 0.2Kg of benzoate, 0.4Kg of imide type compatibilizer, 10Kg of epoxy acrylate, 2-hydroxy-2-methyl-1-phenyl -1-acetone 0.8Kg, organic peroxide 0.8Kg, phosphite antioxidant 0.4Kg weigh each component raw materials, mechanically mix the components evenly;

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.

Step S64: MJP 3D printing molding.

Step S65: directly losing the wax casting, or after cross-linking and solidifying, obtaining a wax mold excellent in mechanical properties for use in making a model.

Comparative example 1:

In Example 3, the photosensitive resin and the photoinitiator were removed.

Comparative example 2:

In Example 3, the photosensitive resin and photoinitiator were replaced with polycarbonate to improve mechanical properties.

Comparative example 3:

In Example 3, the crosslinking agent was removed.

Comparative example 4:

In Example 3, the unsaturated wax was replaced with paraffin wax.

Comparative example 5:

In Example 3, the compatibilizer was removed.

Related performance tests:

The processing characteristics and product properties provided in the above Examples 1-6 and Comparative Examples 1-4 are shown in Table 1.

Table 1 Example and Comparative Processing Characteristics and Product Performance

The above is a detailed description of a 3D printing molding wax which can be cross-linked, has a fast printing speed, a high printing fineness, can be used for casting and a model, and a preparation method thereof. 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 3D printing molding wax which can be crosslinked, has a fast printing speed, and has high printing fineness and can be simultaneously used for casting and modeling, and is characterized in that the following components are included in parts by weight:
The invention relates to a 3D printing molding wax which can be cross-linked, has fast printing speed, high printing fineness and can be used for casting and model simultaneously according to claim 1, wherein the unsaturated wax is polyethylene wax and poly. At least one of propylene waxes wherein the unsaturated wax has a melting temperature of from 65 ° C to 120 ° C.
The 3D printing molding wax which can be cross-linked, has fast printing speed, high printing fineness and can be simultaneously used for casting and modeling according to claim 1, wherein the tackifier is a hydrogenated hydrocarbon resin. At least one of an alicyclic hydrocarbon resin and a hydrogenated rosin ester, wherein the tackifier has a softening temperature of from 90 ° C to 150 ° C.
A 3D printing wax according to claim 1, wherein the nucleating agent is stearate, At least one of sorbitol, benzoate, succinate, glutarate, hexanoate, adipic acid, adipate, benzoate, cinnamate, beta-naphthoate .
The invention relates to a 3D printing molding wax which can be cross-linked, has fast printing speed, high printing fineness and can be used for casting and model simultaneously according to claim 1, wherein the compatibilizing agent is made of unsaturated wax. At least one of a cyclic acid anhydride type compatibilizer, a carboxylic acid type compatibilizer, an epoxy type compatibilizer, an imide type compatibilizer, and an isocyanate type compatibilizer of the substrate.
A 3D printing molding wax which is crosslinkable, has a fast printing speed, is high in print fineness, and can be simultaneously used for casting and modeling according to claim 1, wherein the photosensitive resin is urethane acrylate or epoxy. At least one of acrylate, polyether acrylate, polyester polypropionate, and polyethylene glycol dimethacrylate.
The invention relates to a cross-linkable according to claim 1, a printing speed, a high printing fineness, and can be simultaneously used for casting and molding. Type 3D printing molding wax characterized in that the photoinitiator is 2,4,6 (trimethylbenzoyl)diphenylphosphine oxide, 2,4,6-trimethylbenzoylphosphonic acid Ethyl ester, 2-methyl-1-[4-methylthiophenyl]-2-morpholinyl-1-propanone, 2-isopropylthioxanthone (2,4 isomer mixture, 1-hydroxyl) -cyclohexyl-phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, benzoin dimethyl ether, methyl benzoylbenzoate, benzophenone, 4-chloro Benzophenone, 4-phenylbenzophenone, 2-phenylbenzyl-2-dimethylamine-1-(4-morpholiniumbenzyl)butanone, phenylbis(2,4,6 -trimethylbenzoyl)phosphine oxide, a mixture of benzoylformate, 2-hydroxy-1-(4-(2-hydroxy-2-methylpropionylphenyl)benzyl)-2-methyl- At least one of 1-acetone, bis 2,6-difluoro-3-pyrrolylphenyltitanocene, and 4-dimethylamino-benzoic acid ethyl ester.
The invention relates to a 3D printing molding wax which can be crosslinked, has a fast printing speed, has high printing fineness and can be simultaneously used for casting and modeling according to claim 1, wherein the crosslinking agent is an organic peroxide, At least one of an acid anhydride and a vinyl triethoxysilane.
A 3D printing molding wax which is crosslinkable, has a fast printing speed, is high in print fineness, and can be used for both casting and a model according to claim 1, wherein the antioxidant is hindered phenol and hindered. At least one of an amine, a phosphite, and a sulfate, wherein the complete thermal decomposition temperature of the antioxidant is ≤450 °C.
A method for preparing a cross-linkable, fast printing speed, high printing fineness, and a 3D printing molding wax which can be simultaneously used for casting and modeling according to any one of claims 1 to 9, characterized in that it comprises the following steps :

(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 - 120 ° C to obtain a finished product, wherein the filter paper has a pore size of 0.1 μm - 5 μm;

(4) Printing and molding by MJP 3D printer;

(5) Direct lost wax casting, or after cross-linking and curing, a wax mold excellent in mechanical properties is obtained for use in making a model.